Catalyst compositions comprising chain shuttling agents and the use thereof to produce golf ball compositions

ABSTRACT

The present invention is directed to golf balls having at least one layer which comprises a polymer produced by a process wherein one or more monomers are contacted with a composition comprising the admixture or reaction product resulting from combining (A) a first olefin polymerization catalyst, (B) a second olefin polymerization catalyst capable of preparing polymers differing in chemical or physical properties from the polymer prepared by the first olefin polymerization catalyst under equivalent polymerization conditions, and (C) a chain shuttling agent. Golf balls of the present invention include one-piece, two-piece, and multi-layer golf balls. In two-piece and multi-layer golf balls of the present invention, the polymer may be present in a core layer, a cover layer, an intermediate layer (in the case of multi-layer balls), or a combination thereof.

FIELD OF THE INVENTION

The present invention relates to multi-block copolymers prepared usingcatalyst compositions comprising chain shuttling agents, and to the useof such multi-block copolymers in golf ball compositions.

BACKGROUND OF THE INVENTION

Block copolymers, such as styrene-butadiene andstyrene-butadiene-styrene, are known to be useful in golf ballcompositions. Conventional block copolymers, however, containunsaturated butadiene, and are thus not UV-stable unless the butadieneis hydrogenated to produce a more light stable polymer, such asstyrene-ethylene-butylene-styrene.

Metallocene-catalyzed polymers are also known to be useful in golf ballcompositions. Conventional metallocene polymers, however, generally havea narrow molecular weight distribution, which can lead to inferiorprocessability in golf ball applications compared to polymers having abroad molecular weight distribution. Conventional metallocene polymersalso tend to have poor heat resistance and reduced crystallinity.

Thus, there is a desire in the golf ball industry for novel polymershaving a balance of desirable properties, such as light stability, heatresistance, and flexibility. The present invention describes suchpolymers and their use in a variety of golf ball core, cover, andintermediate layer compositions.

SUMMARY OF THE INVENTION

In one embodiment, the present invention is directed to a golf ballhaving at least one layer formed from a composition comprising amulti-block copolymer, wherein the multi-block copolymer is produced bya process comprising contacting ethylene under addition polymerizationconditions with a catalyst composition. The catalyst compositioncomprises the admixture or reaction product resulting from combining (A)a first olefin polymerization catalyst, (B) a second olefinpolymerization catalyst capable of preparing polymers differing inchemical or physical properties from the polymer prepared by the firstolefin polymerization catalyst under equivalent polymerizationconditions, and (C) a chain shuttling agent. At least one of the firstor second polymerization catalyst is capable of forming a branchedpolymer by means of chain walking or reincorporation of in situ formedolefinic polymer chains.

In another embodiment, the present invention is directed to a golf ballhaving at least one layer formed from a composition comprising amulti-block copolymer, wherein the multi-block copolymer is produced bya process comprising contacting a first monomer selected from propyleneand 4-methyl-1-pentene, and one or more addition polymerizablecomonomers other than the first monomer, under addition polymerizationconditions with a catalyst composition. The catalyst compositioncomprises the admixture or reaction product resulting from combining (A)a first olefin polymerization catalyst, (B) a second olefinpolymerization catalyst capable of preparing polymers differing inchemical or physical properties from the polymer prepared by the firstolefin polymerization catalyst under equivalent polymerizationconditions, and (C) a chain shuttling agent.

In another embodiment, the present invention is directed to a golf ballhaving at least one layer formed from a composition comprising amulti-block copolymer, wherein the multi-block copolymer is produced bya process comprising contacting one or more addition polymerizablemonomers under addition polymerization conditions with a catalystcomposition. The catalyst composition comprises the admixture orreaction product resulting from combining (A) a first olefinpolymerization catalyst, (B) a second olefin polymerization catalystcapable of preparing polymers differing in chemical or physicalproperties from the polymer prepared by the first olefin polymerizationcatalyst under equivalent polymerization conditions, and (C) a chainshuttling agent.

DETAILED DESCRIPTION OF THE INVENTION

Golf balls of the present invention include one-piece, two-piece (i.e.,a core and a cover), multi-layer (i.e., a core of one or more layers anda cover of one or more layers), and wound golf balls, having a varietyof core structures, intermediate layers, covers, and coatings. Golf ballcores may consist of a single, unitary layer, comprising the entire corefrom the center of the core to its outer periphery, or they may consistof a center surrounded by at least one outer core layer. The center,innermost portion of the core may be solid, hollow, or liquid-, gel-, orgas-filled. The outer core layer may be solid, or it may be a woundlayer formed of a tensioned elastomeric material. Golf ball covers mayalso contain one or more layers, such as a double cover having an innerand outer cover layer. Additional layers may optionally be disposedbetween the core and cover. In the golf balls of the present invention,at least one layer is formed from a composition comprising a multi-blockcopolymer, wherein the multi-block copolymer is prepared in the presenceof a chain shuttling agent.

For purposes of the present disclosure, “multi-block copolymer” refersto a polymer comprising two or more chemically, morphologically, orstructurally distinct regions or segments (referred to as “blocks”)preferably joined in a linear manner, that is, a polymer comprisingdifferentiated units which are joined end-to-end with respect topolymerized ethyl enic functionality, rather than in pendent or graftedfashion. In a particular embodiment, the blocks differ in the density,the amount of crystallinity, the crystallite size attributable to apolymer of such composition, the amount of chain branching, thehomogeneity, or any other chemical or physical property attributable toan olefin polymer. In another particular embodiment, the blocks differin the amount or type of comonomer incorporated therein, the density,the amount of crystallinity, the crystallite size attributable to apolymer of such composition, the type or degree of tacticity (isotacticor syndiotactic), regio-regularity or regio-irregularity, the amount ofbranching, including long chain branching or hyperbranching, thehomogeneity, or any other chemical or physical property. In anotherparticular embodiment, the copolymers are characterized by uniquedistributions of both polymer polydispersity (M_(w)/M_(n)), block lengthdistribution, and/or block number distributions. Preferably, whenproduced in a continuous process, the copolymers have a polydispersityof from 1.7 to 2.9, more preferably from 1.8 to 2.5, and most preferablyfrom 1.8 to 2.1. When produced in a batch or semi-batch process, thecopolymers preferably have a polydispersity of from 1.0 to 2.9, morepreferably from 1.3 to 2.5, and most preferably from 1.4 to 1.8.

The term “ethylene multi-block copolymer” means a multi-block copolymercomprising ethylene and optionally one or more copolymerizablecomonomers, wherein ethylene comprises a plurality of the polymerizedmonomer units of at least one block or segment in the polymer,preferably at least 90 mole percent, more preferably at least 95 molepercent, and most preferably at least 98 mole percent of said block.Based on total polymer weight, the ethylene multi-block copolymers ofthe present invention preferably have an ethylene content from 25 to 97percent, more preferably from 40 to 96 percent, even more preferablyfrom 55 to 95 percent, and most preferably from 65 to 85 percent.

The term “comonomer incorporation index” refers to the percent comonomerincorporated into a copolymer prepared under representativeethylene/comonomer polymerization conditions by the catalyst underconsideration in the absence of other polymerization catalysts, ideallyunder steady-state, continuous solution polymerization conditions in ahydrocarbon diluent at 100° C., 4.5 MPa ethylene pressure (reactorpressure), greater than 92 (more preferably greater than 95) percentethylene conversion, and greater than 0.01 percent comonomer conversion.The selection of metal complexes or catalyst compositions having thegreatest difference in comonomer incorporation indices results incopolymers from two or more monomers having the largest difference inblock or segment properties, such as density.

In certain circumstances the comonomer incorporation index may bedetermined directly, for example by the use of NMR spectroscopictechniques. Often, however, any difference in comonomer incorporationmust by indirectly determined. For polymers formed from multiplemonomers this may be accomplished by various techniques based on monomerreactivities.

Comonomer incorporation index and methods for determining relativeamounts of comonomer and monomer in the copolymer are further disclosed,for example, in PCT Publication Nos. WO2005/090425, WO2005/090426, andWO2005/090427, the entire disclosures of which are hereby incorporatedherein by reference.

Monomers

In one embodiment, the copolymer is produced by the polymerization of asingle monomer, ethylene.

In another embodiment, the copolymer is produced by the polymerizationof an addition polymerizable monomer mixture predominantly comprised ofpropylene, 4-methyl-1-pentene, styrene, or another C₄-C₂₀ α-olefin withethylene and/or one or more different addition polymerizable comonomers,especially ethylene and/or one or more C₄-C₂₀ α-olefins, cyclo-olefinsor diolefins, to form a high molecular weight multi-block copolymer.Examples of suitable comonomers include ethylene and straight-chain orbranched C₄-C₃₀ α-olefins (e.g., 1-butene, 1-pentene, 3-methyl-1-butene,1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene,1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene),C₃-C₃₀ cycloolefins (e.g., cyclopentene, cycloheptene, norbornene,5-methyl-2-norbornene, tetracyclododecene, and2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene), di-and poly-olefins (e.g., butadiene, isoprene, 4-methyl-1,3-pentadiene,1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene,1,3-hexadiene, 1,3-octadiene, 1,4-octadiene, 1,5-octadiene,1,6-octadiene, 1,7-octadiene, ethylidene norbornene, vinyl norbornene,dicyclopentadiene, cyclohexadiene, butylidene norbornene,7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, and5,9-dimethyl-1,4,8-decatriene), aromatic vinyl compounds (e.g., mono orpoly alkylstyrenes including styrene, o-methylstyrene, m-methylstyrene,p-methylstyrene, o,p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene,and p-ethylstyrene), and functional group-containing derivatives thereof(e.g., methoxystyrene, ethoxystyrene, vinylbenzoic acid, methylvinylbenzoate, vinylbenzyl acetate, hydroxystyrene, o-chlorostyrene,p-chlorostyrene, divinylbenzene, 3-phenylpropene, 4-phenylpropene,α-methylstyrene, vinylchloride, 1,2-difluoroethylene,1,2-dichloroethylene, tetrafluoroethylene, and3,3,3-trifluoro-1-propene).

In another embodiment, the copolymer is produced by the polymerizationof ethylene and one or more copolymerizable comonomers. Examples ofsuitable comonomers include straight-chain or branched C₃-C₃₀ α-olefins(e.g., propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene,4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene,1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene), andespecially C₄-C₂₀ α-olefins; C₃-C₃₀ cycloolefins, such as those listedabove; di- and poly-olefins, such as those listed above; aromatic vinylcompounds, such as those listed above; and functional group-containingderivatives thereof, such as those listed above.

Suitable monomers and comonomers are further disclosed in PCTPublication Nos. WO2005/090425, WO2005/090426, and WO2005/090427, theentire disclosures of which are hereby incorporated herein by reference.

Chain Shuttling Agents

For purposes of the present disclosure, “shuttling agent” refers to acompound or mixture of compounds employed in catalyst compositions ofthe present invention that is capable of causing polymeryl exchangebetween at least two active catalyst sites of the catalysts included inthe catalyst compositions under the conditions of the polymerization.That is, transfer of a polymer fragment occurs both to and from one ormore of the active catalyst sites. In contrast to a shuttling agent, a“chain transfer agent” causes termination of polymer chain growth andamounts to a one-time transfer of growing polymer from the catalyst tothe transfer agent. Preferably, the shuttling agent has an activityratio R_(A-B)/R_(B-A) of from 0.01 to 100, more preferably from 0.1 to10, more preferably from 0.5 to 2.0, and most preferably from 0.8 to1.2, wherein R_(A-B) is the rate of polymeryl transfer from catalyst Aactive site to catalyst B active site via the shuttling agent, andR_(B-A) is the rate of reverse polymeryl transfer, i.e., the rate ofexchange starting from catalyst B active site to catalyst A active sitevia the shuttling agent. Preferably, the intermediate formed between theshuttling agent and the polymeryl chain is sufficiently stable thatchain termination is relatively rare. Preferably, less than 90 percent,more preferably less than 75 percent, more preferably less than 50percent, and most preferably less than 10 percent, of shuttle-polymerylproducts are terminated prior to attaining 3 distinguishable polymersegments or blocks. Ideally, the rate of chain shuttling (defined by thetime required to transfer a polymer chain from a catalyst site to thechain shuttling agent and then back to a catalyst site) is equivalent toor faster than the rate of polymer termination, even up to 10 or even100 times faster than the rate of polymer termination. This permitspolymer block formation on the same time scale as polymer propagation.

By selecting different combinations of catalysts having differingbranching indices and/or differing comonomer incorporation rates, aswell as differing reactivities, and by pairing various shuttling agentsor mixtures of agents with these catalyst combinations, polymer productscan be prepared having segments of different densities or branchingindices and/or comonomer concentrations, different block lengths, anddifferent numbers of such segments or blocks in each copolymer. Forexample, if the activity of the shuttling agent is low relative to thecatalyst polymer chain propagation rate of one or more of the catalysts,longer block length multi-block copolymers and polymer blends may beobtained. Contrariwise, if shuttling is very fast relative to polymerchain propagation, a copolymer having a more random chain structure andshorter block lengths is obtained. An extremely fast shuttling agent mayproduce a multi-block copolymer having substantially random copolymerproperties. By proper selection of both catalyst mixture and shuttlingagent, relatively pure block copolymers, copolymers containingrelatively large polymer segments or blocks, and/or blends of theforegoing with various ethylene polymers can be obtained.

In one embodiment, a suitable composition comprising Catalyst A,Catalyst B, and a chain shuttling agent can be selected by the followingmulti-step procedure specially adapted for block differentiation basedon branching index:

-   -   I. Ethylene is polymerized using a mixture comprising a        potential catalyst and a potential chain shuttling agent. This        polymerization test is preferably performed using a batch or        semi-batch reactor (that is, without resupply of catalyst or        shuttling agent), preferably with relatively constant ethylene        concentration, operating under solution polymerization        conditions, typically using a molar ratio of catalyst to chain        shuttling agent of from 1:5 to 1:500. After forming a suitable        quantity of polymer, the reaction is terminated by addition of a        catalyst poison and the polymer's properties (branching index,        M_(w), M_(n), and M_(w)/M_(n)) are measured.    -   II. The foregoing polymerization and polymer testing are        repeated for several different reaction times, providing a        series of polymers having a range of yields and polydispersity        values.    -   III. Catalyst/shuttling agent pairs demonstrating significant        polymer transfer both to and from the shuttling agent are        characterized by a polymer series wherein the minimum        polydispersity is less than 2.0, preferably less than 1.5, and        more preferably less than 1.3. Furthermore, if chain shuttling        is occurring, the M_(n) of the polymer will increase, preferably        nearly linearly, as conversion is increased. Preferred        catalyst/shuttling agent pairs are those giving polymer M_(n) as        a function of conversion (or polymer yield) fitting a line with        a statistical precision of greater than 0.95, preferably greater        than 0.99.    -   Steps I-III are then carried out for one or more additional        pairing of potential catalysts and/or putative shuttling agents.    -   A suitable composition comprising Catalyst A, Catalyst B, and        one or more chain shuttling agents is then selected such that        the two catalysts each undergo chain shuttling with one or more        of the chain shuttling agents, and one of the catalysts        (designated as Catalyst B), forms polymer having a higher        branching index compared to Catalyst A under the reaction        conditions chosen. Preferably, at least one of the chain        shuttling agents undergoes polymer transfer in both the forward        and reverse directions (as identified in the foregoing test)        with both Catalyst A and Catalyst B. In addition, the chain        shuttling agent preferably does not reduce the catalyst activity        (measured in weight of polymer produced per weight of catalyst        per unit time) of either catalyst (compared to activity in the        absence of a shuttling agent) by more than 60 percent. More        preferably, such catalyst activity is not reduced by more than        20 percent. Most preferably, the catalyst activity of at least        one of the catalysts is increased compared to the catalyst        activity in the absence of a shuttling agent.    -   Alternatively, suitable catalyst/shuttling agent pairs can be        detected by performing a series of ethylene polymerizations        under standard batch reaction conditions and measuring the        resulting M_(n), polydispersity, branching index, and polymer        yield or production rate. Suitable shuttling agents are        characterized by lowering of the resultant M_(n) without        significant broadening of the polydispersity or loss of activity        (reduction in yield or rate).

In another embodiment, a suitable composition comprising Catalyst A,Catalyst B, and a chain shuttling agent can be selected by the followingmulti-step procedure specially adapted for block differentiation basedon comonomer incorporation:

-   -   I. One or more addition polymerizable monomers, preferably        olefin monomers, are polymerized using a mixture comprising a        potential catalyst and a potential chain shuttling agent. This        polymerization test is preferably performed using a batch or        semi-batch reactor, preferably with relatively constant monomer        concentration, operating under solution polymerization        conditions, typically using a molar ratio of catalyst to chain        shuttling agent of from 1:5 to 1:500. After forming a suitable        quantity of polymer, the reaction is terminated by addition of a        catalyst poison and the polymer's properties (M_(w), M_(n), and        M_(w)/M_(n)) are measured.    -   II. The foregoing polymerization and polymer testing are        repeated for several different reaction times, providing a        series of polymers having a range of yields and polydispersity        values.    -   III. Catalyst/shuttling agent pairs demonstrating significant        polymer transfer both to and from the shuttling agent are        characterized by a polymer series wherein the minimum        polydispersity is less than 2.0, preferably less than 1.5, and        more preferably less than 1.3. Furthermore, if chain shuttling        is occurring, the M_(n) of the polymer will increase, preferably        nearly linearly, as conversion is increased. Preferred        catalyst/shuttling agent pairs are those giving polymer M_(n) as        a function of conversion (or polymer yield) fitting a line with        a statistical precision of greater than 0.95, preferably greater        than 0.99.    -   Steps I-III are then carried out for one or more additional        pairing of potential catalysts and/or putative shuttling agents.    -   A suitable composition comprising Catalyst A, Catalyst B, and        one or more chain shuttling agents is then selected such that        the two catalysts each undergo chain shuttling with one or more        of the chain shuttling agents, and Catalyst A has a higher        comonomer incorporation index (or is otherwise capable of        selectively forming polymer) compared to Catalyst B under the        reaction conditions chosen. Preferably, at least one of the        chain shuttling agents undergoes polymer transfer in both the        forward and reverse directions (as identified in the foregoing        test) with both Catalyst A and Catalyst B. In addition, the        chain shuttling agent preferably does not reduce the catalyst        activity (measured in weight of polymer produced per weight of        catalyst per unit time) of either catalyst (compared to activity        in the absence of a shuttling agent) by more than 60 percent.        More preferably, such catalyst activity is not reduced by more        than 20 percent. Most preferably, the catalyst activity of at        least one of the catalysts is increased compared to the catalyst        activity in the absence of a shuttling agent.    -   Alternatively, suitable catalyst/shuttling agent pairs can be        detected by performing a series of polymerizations under        standard batch reaction conditions and measuring the resulting        M_(n), polydispersity, and polymer yield or production rate.        Suitable shuttling agents are characterized by lowering of the        resultant M_(n) without significant broadening of the        polydispersity or loss of activity (reduction in yield or rate).

Suitable shuttling agents for use herein include Group 1, 2, 12, and 13metal compounds or complexes containing at least one C₁₋₂₀ hydrocarbylgroup, preferably hydrocarbyl substituted aluminum, gallium or zinccompounds containing from 1 to 12 carbons in each hydrocarbyl group, andreaction products thereof with a proton source. Preferred hydrocarbylgroups are alkyl groups, preferably linear or branched C₂₋₈ alkylgroups. Most preferred shuttling agents for use herein are trialkylaluminum and dialkyl zinc compounds, especially triethylaluminum,tri(i-propyl)aluminum, tri(i-butyl)aluminum, tri(n-hexyl)aluminum,tri(n-octyl)aluminum, triethylgallium, and diethylzinc. Additionalsuitable shuttling agents include the reaction product or mixture formedby combining the foregoing organometal compound, preferably a tri(C₁₋₈)alkyl aluminum or di(C₁₋₈) alkyl zinc compound, especiallytriethylaluminum, tri(i-propyl)aluminium, tri(i-butyl)aluminum,tri(n-hexyl)aluminum, tri(n-octyl)aluminum, and diethylzinc, with lessthan a stoichiometric quantity (relative to the number of hydrocarbylgroups) of a secondary amine or a hydroxyl compound, especiallybis(trimethylsilyl)amine, t-butyl(dimethyl)siloxane,2-hydroxymethylpyridine, di(n-pentyl)amine, 2,6-di(t-butyl)phenol,ethyl(1-naphthyl)amine, bis(2,3,6,7-dibenzo-1-azacycloheptaneamine), and2,6-diphenylphenol. Preferably, sufficient amine or hydroxyl reagent isused such that one hydrocarbyl group remains per metal atom. The primaryreaction products of the foregoing combinations most preferable for usein the present invention as shuttling agents are n-octylaluminumdi(bis(trimethylsilyl) amide), i-propylaluminumbis(dimethyl(t-butyl)siloxide), and n-octylaluminumdi(pyridinyl-2-methoxide), i-butylaluminumbis(dimethyl(t-butyl)siloxane), i-butylaluminumbis(di(trimethylsilyl)amide), n-octylaluminum di(pyridine-2-methoxide),i-butylaluminum bis(di(n-pentyl)amide), n-octylaluminumbis(2,6-di-t-butylphenoxide), n-octylaluminumdi(ethyl(1-naphthyl)amide), ethylaluminum bis(t-butyldimethylsiloxide),ethylaluminum di(bis(trimethylsilyl)amide), ethylaluminumbis(2,3,6,7-dibenzo-1-azacycloheptaneamide), n-octylaluminumbis(2,3,6,7-dibenzo-1-azacycloheptaneamide), n-octylaluminumbis(dimethyl(t-butyl)siloxide, ethylzinc (2,6-diphenylphenoxide), andethylzinc (t-butoxide).

Suitable chain shuttling agents are further disclosed in PCT PublicationNos. WO2005/090425, WO2005/090426, and WO2005/090427, the entiredisclosures of which are hereby incorporated herein by reference.

Catalysts

Suitable catalysts for use herein include any compound or combination ofcompounds that is adapted for preparing polymers of the desiredcomposition or type. Both heterogeneous and homogeneous catalysts may beemployed. Examples of heterogeneous catalysts include Ziegler-Nattacompositions, particularly Group 4 metal halides supported on Group 2metal halides or mixed halides and alkoxides and chromium or vanadiumbased catalysts. Preferably, however, for ease of use and for productionof narrow molecular weight polymer segments in solution, the catalystsfor use herein are homogeneous catalysts comprising a relatively pureorganometallic compound or metal complex, especially compounds orcomplexes based on metals selected from Groups 3-10 or the Lanthanideseries of the Periodic Table of the Elements. It is preferred that anycatalyst employed herein not significantly detrimentally affect theperformance of the other catalyst under the conditions of the presentpolymerization. Preferably, no catalyst is reduced in activity bygreater than 25 percent, more preferably greater than 10 percent, underthe conditions of the present polymerization.

Metal complexes for use herein as Catalyst A include complexes oftransition metals selected from Groups 3 to 15 of the Period Table ofthe Elements containing one or more delocalized, π-bonded ligands orpolyvalent Lewis base ligands. Examples include metallocene,half-metallocene, constrained geometry, and polyvalent pyridylamine, orother polychelating base complexes. The complexes are genericallydepicted by the formula: MK_(k)X_(x)Z_(z), or a dimer thereof wherein:

-   -   M is a metal selected from Groups 3-15, preferably 3-10, more        preferably 4-8, and most preferably Group 4 of the Periodic        Table of the Elements;    -   K independently each occurrence is a group containing        delocalized π-electrons or one or more electron pairs through        which K is bound to M, said K group containing up to 50 atoms        not counting hydrogen atoms, optionally two or more K groups may        be joined together forming a bridged structure, and further        optionally one or more K groups may be bound to Z, to X, or to        both Z and X;    -   X independently each occurrence is a monovalent, anionic moiety        having up to 40 non-hydrogen atoms, optionally one or more X        groups may be bonded together thereby forming a divalent or        polyvalent anionic group, and further optionally one or more X        groups and one or more Z groups may be bonded together thereby        forming a moiety that is both covalently bound to M and        coordinated thereto;    -   Z independently each occurrence is a neutral, Lewis base donor        ligand of up to 50 non-hydrogen atoms containing at least one        unshared electron pair through which Z is coordinated to M;    -   k is an integer from 0 to 3;    -   x is an integer from 1 to 4;    -   z is a number from 0 to 3; and    -   the sum, k+x, is equal to the formal oxidation state of M.

Suitable metal complexes include those containing from 1 to 3 π-bondedanionic or neutral ligand groups, which may be cyclic or non-cyclicdelocalized π-bonded anionic ligand groups. Exemplary of such π-bondedgroups are conjugated and nonconjugated, cyclic and non-cyclic diene anddienyl groups, allyl groups, boratabenzene groups, phosphole, and arenegroups. By the term “π-bonded” it is meant that the ligand group isbonded to the transition metal by a sharing of electrons from apartially delocalized π-bond.

Each atom in the delocalized π-bonded group may independently besubstituted with a radical selected from the group consisting ofhydrogen, halogen, hydrocarbyl, halohydrocarbyl, hydrocarbyl-substitutedheteroatoms where the heteroatom is selected from Group 14-16 of thePeriodic Table of the Elements, and such hydrocarbyl-substitutedheteroatom radicals further substituted with a Group 15 or 16 heteroatom containing moiety. In addition, two or more such radicals maytogether form a fused ring system, including partially or fullyhydrogenated fused ring systems, or they may form a metallocycle withthe metal. Included within the term “hydrocarbyl” are C₁-C₂₀ straight,branched and cyclic alkyl radicals, C₆-C₂₀ aromatic radicals, C₇-C₂₀alkyl-substituted aromatic radicals, and C₇-C₂₀ aryl-substituted alkylradicals. Suitable hydrocarbyl-substituted heteroatom radicals includemono-, di- and tri-substituted radicals of boron, silicon, germanium,nitrogen, phosphorus and oxygen wherein each of the hydrocarbyl groupscontains from 1 to 20 carbon atoms. Examples include N,N-dimethylamino,pyrrolidinyl, trimethylsilyl, triethylsilyl, t-butyldimethylsilyl,methyldi(t-butyl)silyl, triphenylgermyl, and trimethylgermyl groups.Examples of Group 15 and 16 hetero atom containing moieties includeamino, phosphino, alkoxy, and alkylthio moieties or divalent derivativesthereof, for example, amide, phosphide, alkyleneoxy or alkylenethiogroups bonded to the transition metal or Lanthanide metal, and bonded tothe hydrocarbyl group, π-bonded group, or hydrocarbyl-substitutedheteroatom.

Examples of suitable anionic, delocalized π-bonded groups includecyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl,tetrahydrofluorenyl, octahydrofluorenyl, pentadienyl, cyclohexadienyl,dihydroanthracenyl, hexahydroanthracenyl, decahydroanthracenyl groups,phosphole, and boratabenzyl groups, as well as inertly substitutedderivatives thereof, especially C₁-C₁₀ hydrocarbyl-substituted ortris(C₁-C₁₀ hydrocarbyl)silyl-substituted derivatives thereof. Preferredanionic delocalized 1-bonded groups are cyclopentadienyl,pentamethylcyclopentadienyl, tetramethylcyclopentadienyl,tetramethylsilylcyclopentadienyl, indenyl, 2,3-dimethylindenyl,fluorenyl, 2-methylindenyl, 2-methyl-4-phenylindenyl,tetrahydrofluorenyl, octahydrofluorenyl, 1-indacenyl,3-pyrrolidinoinden-1-yl, 3,4-(cylcopenta(l)phenanthren1-yl, andtetrahydroindenyl.

Boratabenzyl ligands are anionic ligands which are boron containinganalogues to benzene, and are further described, for example, by G.Herberich, et al., in Organometallics, 14, 1, 471-480 (1995), the entiredisclosure of which is hereby incorporated herein by reference.

Phospholes are anionic ligands that are phosphorus containing analoguesto a cyclopentadienyl group, and are further described, for example, inPCT Publication No. WO 98/50392, the entire disclosure of which ishereby incorporated herein by reference.

Preferred transition metal complexes for use herein correspond to theformula: MK_(k)X_(x)Z_(z), or a dimer thereof, wherein:

-   -   M is a Group 4 metal;    -   K is a group containing delocalized π-electrons through which K        is bound to M, said K group containing up to 50 atoms not        counting hydrogen atoms, optionally two K groups may be joined        together forming a bridged structure, and further optionally one        K may be bound to X or Z;    -   X each occurrence is a monovalent, anionic moiety having up to        40 non-hydrogen atoms, optionally one or more X and one or more        K groups are bonded together to form a metallocycle, and further        optionally one or more X and one or more Z groups are bonded        together thereby forming a moiety that is both covalently bound        to M and coordinated thereto;    -   Z independently each occurrence is a neutral, Lewis base donor        ligand of up to 50 non-hydrogen atoms containing at least one        unshared electron pair through which Z is coordinated to M;    -   k is an integer from 0 to 3;    -   x is an integer from 1 to 4;    -   z is a number from 0 to 3; and    -   the sum, k+x, is equal to the formal oxidation state of M.

Preferred complexes include those containing either one or two K groups.The latter complexes include those containing a bridging group linkingthe two K groups. Preferred bridging groups are those corresponding tothe formula (ER′₂)_(e) wherein E is silicon, germanium, tin, or carbon,R′ independently each occurrence is hydrogen or a group selected fromsilyl, hydrocarbyl, hydrocarbyloxy and combinations thereof, said R′having up to 30 carbon or silicon atoms, and e is 1 to 8. Preferably, R′independently each occurrence is methyl, ethyl, propyl, benzyl,tert-butyl, phenyl, methoxy, ethoxy or phenoxy. In some embodiments,racemic ethylene bisindenyl complexes of Group 4 metals, especially Zr,and inertly substituted derivatives thereof, such as 1-, or2-t-butyldimethylsiloxy-substituted ethylene bis(indenyl)zirconiumcomplexes, as disclosed in Macromolecules 33, 9200-9204 (2000),ethylenebis(4,5,6,7-tetrahydro-1-indenyl) zirconium complexes, or otherracemic ethylene bis(indenyl)zirconium complexes capable of 2,1- or3,1-monomer insertion or chain walking are usefully employed.

Examples of suitable metal complexes of the foregoing formula arefurther disclosed in PCT Publication Nos. WO2005/090425, WO2005/090426,and WO2005/090427, the entire disclosures of which are herebyincorporated herein by reference.

A further class of suitable metal complexes for use herein correspondsto the formula: MKZ_(z)X_(x), or a dimer thereof, wherein M, K, X, x andz are as previously defined, and Z is a substituent of up to 50non-hydrogen atoms that together with K forms a metallocycle with M.Preferred Z substituents include groups containing up to 30 non-hydrogenatoms comprising at least one atom that is oxygen, sulfur, boron or amember of Group 14 of the Periodic Table of the Elements directlyattached to K, and a different atom, selected from the group consistingof nitrogen, phosphorus, oxygen or sulfur that is covalently bonded toM. This class of Group 4 metal complexes includes “constrained geometrycatalysts,” as further disclosed in PCT Publication Nos. WO2005/090425,WO2005/090426, and WO2005/090427, the entire disclosures of which arehereby incorporated herein by reference.

Additional examples of suitable metal complexes for use herein ascatalyst (A) are polycyclic complexes corresponding to the formula:

-   -   where M is titanium in the +2, +3 or +4 formal oxidation state;    -   R⁷ independently each occurrence is hydride, hydrocarbyl, silyl,        germyl, halide, hydrocarbyloxy, hydrocarbylsiloxy,        hydrocarbylsilylamino, di(hydrocarbyl)amino,        hydrocarbyleneamino, di(hydrocarbyl)phosphino,        hydrocarbylene-phosphino, hydrocarbylsulfido, halo-substituted        hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl,        silyl-substituted hydrocarbyl, hydrocarbylsiloxy-substituted        hydrocarbyl, hydrocarbylsilylamino-substituted hydrocarbyl,        di(hydrocarbyl)amino-substituted hydrocarbyl,        hydrocarbyleneamino-substituted hydrocarbyl,        di(hydrocarbyl)phosphino-substituted hydrocarbyl,        hydrocarbylene-phosphino-substituted hydrocarbyl, or        hydrocarbylsulfido-substituted hydrocarbyl, said R⁷ group having        up to 40 atoms not counting hydrogen, and optionally two or more        of the foregoing groups may together form a divalent derivative;    -   R⁸ is a divalent hydrocarbylene or substituted hydrocarbylene        group forming a fused system with the remainder of the metal        complex, said R⁸ containing from 1 to 30 atoms not counting        hydrogen;    -   X^(a) is a divalent moiety, or a moiety comprising one σ-bond        and a neutral two electron pair able to form a        coordinate-covalent bond to M, said X^(a) comprising boron, or a        member of Group 14 of the Periodic Table of the Elements, and        also comprising nitrogen, phosphorus, sulfur or oxygen;    -   X is a monovalent anionic ligand group having up to 60 atoms        exclusive of the class of ligands that are cyclic, delocalized,        π-bound ligand groups and optionally two X groups together form        a divalent ligand group;    -   Z independently each occurrence is a neutral ligating compound        having up to 20 atoms;    -   x is 0, 1 or 2; and    -   z is 0 or 1.

Additional examples of suitable metal complexes for use herein ascatalyst (A) include those of the formula:

Further illustrative examples of metal complexes for use hereincorrespond to the formula:

-   -   where M is titanium in the +2, +3 or +4 formal oxidation state;    -   T is —NR⁹— or —O—;    -   R⁹ is hydrocarbyl, silyl, germyl, dihydrocarbylboryl, or        halohydrocarbyl or up to 10 atoms not counting hydrogen;    -   R¹⁰ independently each occurrence is hydrogen, hydrocarbyl,        trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, germyl,        halide, hydrocarbyloxy, hydrocarbylsiloxy,        hydrocarbylsilylamino, di(hydrocarbyl)amino,        hydrocarbyleneamino, di(hydrocarbyl)phosphino,        hydrocarbylene-phosphino, hydrocarbylsulfido, halo-substituted        hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl,        silyl-substituted hydrocarbyl, hydrocarbylsiloxy-substituted        hydrocarbyl, hydrocarbylsilylamino-substituted hydrocarbyl,        di(hydrocarbyl)amino-substituted hydrocarbyl,        hydrocarbyleneamino-substituted hydrocarbyl,        di(hydrocarbyl)phosphino-substituted hydrocarbyl,        hydrocarbylenephosphino-substituted hydrocarbyl, or        hydrocarbylsulfido-substituted hydrocarbyl, said R¹⁰ group        having up to 40 atoms not counting hydrogen atoms, and        optionally two or more of the foregoing adjacent R¹⁰ groups may        together form a divalent derivative thereby forming a saturated        or unsaturated fused ring;    -   X^(a) is a divalent moiety lacking in delocalized π-electrons,        or such a moiety comprising one σ-bond and a neutral two        electron pair able to form a coordinate-covalent bond to M, said        X^(a) comprising boron, or a member of Group 14 of the Periodic        Table of the Elements, and also comprising nitrogen, phosphorus,        sulfur or oxygen;    -   X is a monovalent anionic ligand group having up to 60 atoms        exclusive of the class of ligands that are cyclic ligand groups        bound to M through delocalized π-electrons or two X groups        together are a divalent anionic ligand group;    -   Z independently each occurrence is a neutral ligating compound        having up to 20 atoms;    -   x is 0, 1, 2 or 3; and    -   z is 0 or 1.

Highly preferably T is ═N(CH₃), X is halo or hydrocarbyl, x is 2, X^(a)is dimethylsilane, z is 0, and R¹⁰) each occurrence is hydrogen, ahydrocarbyl, hydrocarbyloxy, dihydrocarbylamino, hydrocarbyleneamino,dihydrocarbylamino-substituted hydrocarbyl group, orhydrocarbyleneamino-substituted hydrocarbyl group of up to 20 atoms notcounting hydrogen, and optionally two R¹⁰ groups may be joined together.

Illustrative metal complexes of the foregoing formula that may beemployed herein further include those disclosed in PCT Publication Nos.WO2005/090425, WO2005/090426, and WO2005/090427, the entire disclosuresof which are hereby incorporated herein by reference.

Other delocalized, π-bonded complexes, especially those containing otherGroup 4 metals, will be apparent to those skilled in the art, and aredisclosed among other places in PCT Publication Nos. WO2003/78480,WO2003/78483, WO2002/92610, and WO2002/02577; U.S. patent applicationPublication No. 2003/0004286; and U.S. Pat. Nos. 6,515,155, 6,555,634,6,150,297, 6,034,022, 6,268,444, 6,015,868, 5,866,704, and 5,470,993.The entire disclosure of each of these references is hereby incorporatedherein by reference.

Additional examples of metal complexes that are usefully employed hereinas catalyst (A) are complexes of polyvalent Lewis bases, such ascompounds corresponding to the formula:

-   -   wherein T^(b) is a bridging group, preferably containing 2 or        more atoms other than hydrogen;    -   X^(b) and Y^(b) are each independently selected from the group        consisting of nitrogen, sulfur, oxygen and phosphorus; more        preferably both X^(b) and Y^(b) are nitrogen;    -   R^(b) and R^(b′) independently each occurrence are hydrogen or        C₁-C₅₀ hydrocarbyl groups optionally containing one or more        heteroatoms or inertly substituted derivative thereof.        Non-limiting examples of suitable R^(b) and R^(b′) groups        include alkyl, alkenyl, aryl, aralkyl, (poly)alkylaryl and        cycloalkyl groups, as well as nitrogen, phosphorus, oxygen and        halogen substituted derivatives thereof. Specific examples of        suitable R^(b) and R^(b′) groups include methyl, ethyl,        isopropyl, octyl, phenyl, 2,6-dimethylphenyl,        2,6-di(isopropyl)phenyl, 2,4,6-trimethylphenyl,        pentafluorophenyl, 3,5-trifluoromethylphenyl, and benzyl;    -   g is 0 or 1;    -   M^(b) is a metallic element selected from Groups 3-15, or the        Lanthanide series of the Periodic Table of the Elements.        Preferably M^(b) is a Group 3-13 metal, more preferably M^(b) is        a Group 4-10 metal;    -   L^(b) is a monovalent, divalent, or trivalent anionic ligand        containing from 1 to 50 atoms, not counting hydrogen. Examples        of suitable L^(b) groups include halide; hydride; hydrocarbyl,        hydrocarbyloxy; di(hydrocarbyl)amido, hydrocarbyleneamido,        di(hydrocarbyl)phosphido; hydrocarbylsulfido; hydrocarbyloxy,        tri(hydrocarbylsily)alkyl; and carboxylates. More preferred        L^(b) groups are C₁-C₂₀ alkyl, C₇-C₂₀ aralkyl, and chloride;    -   h is an integer from 1 to 6, preferably from 1 to 4, more        preferably from 1 to 3, and j is 1 or 2, with the value h×j        selected to provide charge balance;    -   Z^(b) is a neutral ligand group coordinated to M^(b), and        containing up to 50 atoms not counting hydrogen. Preferred Z^(b)        groups include aliphatic and aromatic amines, phosphines, and        ethers, alkenes, alkadienes, and inertly substituted derivatives        thereof. Suitable inert substituents include halogen, alkoxy,        aryloxy, alkoxycarbonyl, aryloxycarbonyl, di(hydrocarbyl)amine,        tri(hydrocarbylsilyl, and nitrile groups. Preferred Z^(b) groups        include triphenylphosphine, tetrahydrofuran, pyridine, and        1,4-diphenylbutadiene;    -   f is an integer from 1 to 3;    -   two or three of T^(b), R^(b), and R^(b′) may be joined together        to form a single or multiple ring structure;    -   h is an integer from 1 to 6, preferably from 1 to 4, more        preferably from 1 to 3;    -   indicates any form of electronic interaction, especially        coordinate or covalent bonds, including multiple bonds, arrows        signify coordinate bonds, and dotted lines indicate optional        double bonds.

In one embodiment, it is preferred that R^(b) have relatively low sterichindrance with respect to X^(b). In this embodiment, most preferredR^(b) groups are straight chain alkyl groups, straight chain alkenylgroups, branched chain alkyl groups wherein the closest branching pointis at least 3 atoms removed from X^(b), and halo, dihydrocarbylamino,alkoxy or trihydrocarbylsilyl substituted derivatives thereof. Highlypreferred R^(b) groups in this embodiment are C₁-C₈ straight chain alkylgroups.

At the same time, in this embodiment R^(b′) preferably has relativelyhigh steric hindrance with respect to Y^(b). Non-limiting examples ofsuitable R^(b′) groups for this embodiment include alkyl or alkenylgroups containing one or more secondary or tertiary carbon centers,cycloalkyl, aryl, alkaryl, aliphatic or aromatic heterocyclic groups,organic or inorganic oligomeric, polymeric or cyclic groups, and halo,dihydrocarbylamino, alkoxy or trihydrocarbylsilyl substitutedderivatives thereof. Preferred R^(b′) groups in this embodiment containfrom 3 to 40, more preferably from 3 to 30, and most preferably from 4to 20 atoms not counting hydrogen and are branched or cyclic.

Examples of preferred T^(b) groups are structures corresponding to thefollowing formulas:

wherein

each R^(d) is C₁-C₁₀ hydrocarbyl group, preferably methyl, ethyl,n-propyl, i-propyl, t-butyl, phenyl, 2,6-dimethylphenyl, benzyl, ortolyl. Each R^(e) is C₁-C₁₀ hydrocarbyl group, preferably methyl, ethyl,n-propyl, i-propyl, t-butyl, phenyl, 2,6-dimethylphenyl, benzyl, ortolyl. In addition, two or more R^(d) or R_(e) groups, or mixtures ofR^(d) and R_(e) groups may together form a polyvalent derivative of ahydrocarbyl group, such as 1,4-butylene, 1,5-pentylene, or amulticyclic, fused ring, polyvalent hydrocarbyl- orheterohydrocarbyl-group, such as naphthalene-1,8-diyl.

Preferred examples of the foregoing polyvalent Lewis base complexesfurther include those disclosed in PCT Publication Nos. WO2005/090425,WO2005/090426, and WO2005/090427, the entire disclosures of which arehereby incorporated herein by reference.

Highly preferred metal complexes for use herein as catalyst (A)correspond to the formula:

-   -   wherein X¹ each occurrence is halide, N,N-dimethylamido, or        C₁-C₄ alkyl, and preferably each occurrence X¹ is methyl;    -   R^(f) independently each occurrence is hydrogen, halogen, C₁-C₂₀        alkyl or C₆-C₂₀ aryl, or two adjacent R^(f) groups are joined        together thereby forming a ring, and f is 1-5; and    -   R^(c) independently each occurrence is hydrogen, halogen, C₁-C₂₀        alkyl, or C₆-C₂₀ aryl, or two adjacent R^(c) groups are joined        together thereby forming a ring, and c is 1-5.

Most highly preferred examples of metal complexes for use herein ascatalyst (A) are complexes of the following formulas:

-   -   wherein Rx is C₁-C₄ alkyl or cycloalkyl, preferably methyl,        isopropyl, t-butyl or cyclohexyl; and    -   X¹ each occurrence is halide, N,N-dimethylamido, or C₁-C₄ alkyl,        preferably methyl.

Under the reaction conditions used to prepare the metal complexes usedherein, the hydrogen of the 2-position of the α-naphthalene groupsubstituted at the 6-position of the pyridin-2-yl group is subject toelimination, thereby uniquely forming metal complexes wherein the metalis covalently bonded to both the resulting amide group and to the2-position of the α-naphthalenyl group, as well as stabilized bycoordination to the pyridinyl nitrogen atom through the electron pair ofthe nitrogen atom.

Additional suitable metal complexes of polyvalent Lewis bases for useherein include compounds corresponding to the formula:

-   -   R²⁰ is an aromatic or inertly substituted aromatic group        containing from 5 to 20 atoms not counting hydrogen, or a        polyvalent derivative thereof;    -   T³ is a hydrocarbylene or silane group having from 1 to 20 atoms        not counting hydrogen, or an inertly substituted derivative        thereof;    -   M³ is a Group 4 metal, preferably zirconium or hafnium;    -   G is an anionic, neutral or dianionic ligand group; preferably a        halide, hydrocarbyl or dihydrocarbylamide group having up to 20        atoms not counting hydrogen;    -   g is a number from 1 to 5 indicating the number of such G        groups; and    -   bonds and electron donative interactions are represented by        lines and arrows respectively.

The foregoing polyvalent Lewis base complexes are conveniently preparedby standard metallation and ligand exchange procedures involving asource of the Group 4 metal and the neutral polyfunctional ligandsource. In addition, the complexes may also be prepared by means of anamide elimination and hydrocarbylation process starting from thecorresponding Group 4 metal tetraamide and a hydrocarbylating agent,such as trimethylaluminum. Other techniques may be used as well. Thesecomplexes are known from the disclosures of, among others, U.S. Pat.Nos. 6,320,005 and 6,103,657, PCT Publication Nos. WO2002/38628 andWO2003/40195, and U.S. patent application Publication No. 2004/0220050,the entire disclosures of which are hereby incorporated herein byreference.

Additional examples of suitable metal complexes are aromatic dioxyiminecomplexes of zirconium, corresponding to the formula:

-   -   wherein X² is as previously defined, preferably C₁-C₁₀        hydrocarbyl, most preferably methyl or benzyl; and    -   R^(e′) is methyl, isopropyl, t-butyl, cyclopentyl, cyclohexyl,        2-methylcyclohexyl, 2,4-dimethylcyclohexyl, 2-pyrrolyl,        N-methyl-2-pyrrolyl, 2-piperidenyl, N-methyl-2-piperidenyl,        benzyl, o-tolyl, 2,6-dimethylphenyl, perfluorophenyl,        2,6-di(isopropyl)phenyl, or 2,4,6-trimethylphenyl.

Also suitable are the catalysts previously disclosed in J. Am. Chem.Soc., 118, 267-268 (1996), J. Am. Chem. Soc., 117, 6414-6415 (1995), andOrganometallics, 16, 1514-1516 (1997), among other disclosures. Theentire disclosure of each of these references is hereby incorporatedherein by reference.

Additional suitable metal complexes include metal complexescorresponding to the formula:

-   -   where M′ is a metal of Groups 4-13, preferably Groups 8-10, most        preferably Ni or Pd;    -   R^(A), R^(B) and R^(C) are univalent or neutral substituents,        which also may be joined together to form one or more divalent        substituents, and    -   c is a number chosen to balance the charge of the metal complex.

Preferred examples of the foregoing metal complexes are furtherdisclosed in PCT Publication No. WO2005/090426, the entire disclosure ofwhich is hereby incorporated herein by reference.

In embodiments wherein the copolymer is produced by the polymerizationof a single monomer, ethylene, suitable metal compounds for use ascatalyst (B) include the foregoing metal compounds mentioned withrespect to catalyst (A) as well as other metal compounds, with theproviso that they result in formation of at least some hyperbranch- orlong chain branch-formation. In such embodiments, the following metalcompounds or inertly coordinated derivatives thereof are especiallysuited for use as catalyst (B): racemic ethylene bisindenyl complexes ofGroup 4 metals, especially Zr, and inertly substituted derivativesthereof, such as 1-, or 2-t-butyldimethylsiloxy-substituted ethylenebis(indenyl)zirconium complexes, as disclosed in Macromolecules 33,9200-9204 (2000), ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium-complexes racemic ethylene bis(indenyl)zirconium complexes,and metal complexes of the formula:

-   -   where M′ is a metal of Groups 4-13, preferably Groups 8-10, most        preferably Ni or Pd;    -   R^(A), R^(B) and R^(C) are univalent or neutral substituents,        which also may be joined together to form one or more divalent        substituents, and    -   c is a number chosen to balance the charge of the metal complex.        Preferred examples of the foregoing metal complexes for use as        catalyst (B) are compounds corresponding to the formula:

-   -   wherein M′ is Pd or Ni.

In embodiments wherein the copolymer is produced by the polymerizationof an addition polymerizable monomer mixture predominantly comprised ofpropylene, 4-methyl-1-pentene, styrene, or another C₄-C₂₀ α-olefin withethylene and/or one or more different addition polymerizable comonomers,suitable metal compounds for use as catalyst (B) include the foregoingmetal compounds mentioned with respect to catalyst (A) as well as othermetal compounds, with the proviso, in a particular embodiment, that theyincorporate comonomer relatively poorly compared to catalyst (A) orotherwise produce a more highly tactic polymer. In such embodiments, thefollowing metal compounds or inertly coordinated derivatives thereof areespecially suited for use as catalyst (B): racemic ethylene bisindenyl-or substituted bis(indenyl)-complexes of Group 4 metals, especially Zr,such as ethylenebis(4,5,6,7-tetrahydro-1-indenyl) zirconium- or racemicethylene bis(indenyl)zirconium-complexes.

In embodiments wherein the copolymer is produced by the polymerizationof ethylene and one or more copolymerizable comonomers, suitable metalcompounds for use as catalyst (B) include the foregoing metal compoundsmentioned with respect to catalyst (A) as well as other metal compounds,with the proviso, in a particular embodiment, that they incorporatecomonomer relatively poorly compared to catalyst (A). In suchembodiments, the following metal compounds are especially suited for useas catalyst (B):

Group 4-10 derivatives corresponding to the formula:

-   -   wherein M² is a metal of Groups 4-10 of the Periodic Table of        the Elements, preferably Group 4 metals, Ni(II) or Pd(II), most        preferably zirconium;    -   T² is a nitrogen, oxygen or phosphorus containing group;    -   X² is a halo, hydrocarbyl, or hydrocarbyloxy;    -   t is one or two;    -   x″ is a number selected to provide charge balance;    -   and T² and N are linked by a bridging ligand.        Such catalysts have been previously disclosed in J. Am. Chem.        Soc., 118, 267-268 (1996), J. Am. Chem. Soc., 117,        6414-6415 (1995) and Organometallics, 16, 1514-1516 (1997),        among other disclosures. Preferred examples of the foregoing        metal complexes for use as catalyst (B) are aromatic diimine or        aromatic dioxyimine complexes of Group 4 metals, especially        zirconium, corresponding to the formula:

-   -   wherein M², X² and T² are as previously defined    -   R^(d) independently each occurrence is hydrogen, halogen, or        R^(e); and    -   R^(e) independently each occurrence is C₁-C₂₀ hydrocarbyl or a        heteroatom-, especially a F, N, S or P-substituted derivative        thereof, more preferably C₁-C₁₀ hydrocarbyl or a F or N        substituted derivative thereof, most preferably alkyl,        dialkylaminoalkyl, pyrrolyl, piperidenyl, perfluorophenyl,        cycloalkyl, (poly)alkylaryl, or aralkyl.        Most preferred examples of the foregoing metal complexes for use        as catalyst (B) are aromatic dioxyimine complexes of zirconium,        corresponding to the formula:

-   -   wherein X² is as previously defined, preferably C₁-C₁₀        hydrocarbyl, most preferably methyl or benzyl; and    -   R^(e′) is methyl, isopropyl, t-butyl, cyclopentyl, cyclohexyl,        2-methylcyclohexyl, 2,4-dimethylcyclohexyl, 2-pyrrolyl,        N-methyl-2-pyrrolyl, 2-piperidenyl, N-methyl-2-piperidenyl,        benzyl, o-tolyl, 2,6-dimethylphenyl, perfluorophenyl,        2,6-di(isopropyl)phenyl, or 2,4,6-trimethylphenyl.        The foregoing complexes for use as catalyst (B) also include        certain phosphinimine complexes as disclosed in European        Publication EP-A-890581, the entire disclosure of which is        hereby incorporated herein by reference. These complexes        correspond to the formula:        [(R^(f))₃—P═N]_(f)M(K²)(R^(f))_(3-f),    -   wherein R^(f) is a monovalent ligand or two R^(f) groups        together are a divalent ligand, preferably R^(f) is hydrogen or        C₁-C₄ alkyl;    -   M is a Group 4 metal,    -   K² is a group containing delocalized π-electrons through which        K² is bound to M, said K² group containing up to 50 atoms not        counting hydrogen atoms, and    -   f is 1 or 2.

The skilled artisan will appreciate that in other embodiments of theinvention, the criterion for selecting a combination of catalyst (A) and(B) may be any other distinguishing property of the resulting polymerblocks, such as combinations based on tacticity (isotactic/syndiotactic,isotactic/atactic or syndiotactic/atactic), regio-error content, orcombinations thereof, for example atactic blocks withregio-error-containing blocks or atactic blocks with long chain branchedblocks.

Suitable catalysts are further described in PCT Publication Nos.WO2005/090425, WO2005/090426, and WO2005/090427, the entire disclosuresof which are hereby incorporated herein by reference.

Cocatalysts

Each of the metal complex catalysts (A) and (B) may be activated to formthe active catalyst composition by combination with a cocatalyst,preferably a cation forming cocatalyst, a strong Lewis acid, or acombination thereof. In a preferred embodiment, the shuttling agent isemployed both for purposes of chain shuttling and as the cocatalystcomponent of the catalyst composition.

The metal complexes desirably are rendered catalytically active bycombination with a cation forming cocatalyst, such as those previouslyknown in the art for use with Group 4 metal olefin polymerizationcomplexes. Suitable cation forming cocatalysts for use herein includeneutral Lewis acids, such as C₁-C₃₀ hydrocarbyl substituted Group 13compounds, especially tri(hydrocarbyl)aluminum- or tri(hydrocarbyl)boroncompounds and halogenated (including perhalogenated) derivativesthereof, having from 1 to 10 carbons in each hydrocarbyl or halogenatedhydrocarbyl group, more especially perfluorinated tri(aryl) boroncompounds, and most especially tris(pentafluoro-phenyl)borane;nonpolymeric, compatible, noncoordinating, ion forming compounds(including the use of such compounds under oxidizing conditions),especially the use of ammonium-, phosphoniurn-, oxonium-, carbonium-,silylium- or sulfonium-salts of compatible, noncoordinating anions, orferrocenium-, lead- or silver salts of compatible, noncoordinatinganions; and combinations of the foregoing cation forming cocatalysts andtechniques. The foregoing activating cocatalysts and activatingtechniques have been previously taught with respect to different metalcomplexes for olefin polymerizations, for example, in the followingreferences: European Publication EP-A-277003; U.S. Pat. Nos. 5,153,157,5,064,802, 5,321,106, 5,721,185, 5,350,723, 5,425,872, 5,625,087,5,883,204, and 5,919,983, 5,783,512; and PCT Publication Nos. WO99/15534and WO99/42467, the entire disclosures of which are hereby incorporatedherein by reference.

Combinations of neutral Lewis acids, especially the combination of atrialkyl aluminum compound having from 1 to 4 carbons in each alkylgroup and a halogenated tri(hydrocarbyl)boron compound having from 1 to20 carbons in each hydrocarbyl group, especiallytrispentafluorophenyl)borane, further combinations of such neutral Lewisacid mixtures with a polymeric or oligomeric alumoxane, and combinationsof a single neutral Lewis acid, especially tris(pentafluorophenyl)boranewith a polymeric or oligomeric alumoxane may be used as activatingcocatalysts. Preferred molar ratios of metalcomplex:tris(pentafluorophenyl-borane):alumoxane are from 1:1:1 to1:5:20, more preferably from 1:1:1.5 to 1:5:10.

In one embodiment, suitable ion forming compounds useful as cocatalystscomprise a cation which is a Bronsted acid capable of donating a proton,and a compatible, noncoordinating anion, A⁻. As used herein, the term“noncoordinating” means an anion or substance which either does notcoordinate to the Group 4 metal containing precursor complex and thecatalytic derivative derived therefrom, or which is only weaklycoordinated to such complexes thereby remaining sufficiently labile tobe displaced by a neutral Lewis base. A noncoordinating anionspecifically refers to an anion which when functioning as a chargebalancing anion in a cationic metal complex does not transfer an anionicsubstituent or fragment thereof to said cation thereby forming neutralcomplexes. “Compatible anions” are anions which are not degraded toneutrality when the initially formed complex decomposes and arenoninterfering with desired subsequent polymerization or other uses ofthe complex.

Preferred anions are those containing a single coordination complexcomprising a charge-bearing metal or metalloid core which anion iscapable of balancing the charge of the active catalyst species (themetal cation) which may be formed when the two components are combined.Also, said anion should be sufficiently labile to be displaced byolefinic, diolefinic and acetylenically unsaturated compounds or otherneutral Lewis bases such as ethers or nitrites. Suitable metals include,but are not limited to, aluminum, gold and platinum. Suitable metalloidsinclude, but are not limited to, boron, phosphorus, and silicon.Compounds containing anions which comprise coordination complexescontaining a single metal or metalloid atom are well known and many,particularly such compounds containing a single boron atom in the anionportion, are available commercially.

Preferably, such cocatalysts may be represented by the following generalformula:(L*-H)_(g) ⁺(A)^(g−)

-   -   wherein L* is a neutral Lewis base;    -   (L*-H)⁺ is a conjugate Bronsted acid of L*;    -   A^(g−) is a noncoordinating, compatible anion having a charge of        g−, and    -   g is an integer from 1 to 3.

More preferably A^(g−) corresponds to the formula:[M′Q₄]⁻

-   -   wherein M′ is boron or aluminum in the +3 formal oxidation        state; and    -   Q independently each occurrence is selected from hydride,        dialkylamido, halide, hydrocarbyl, hydrocarbyloxide,        halosubstituted-hydrocarbyl, halosubstituted hydrocarbyloxy, and        halo-substituted silylhydrocarbyl radicals (including        perhalogenated hydrocarbyl-perhalogenated hydrocarbyloxy- and        perhalogenated silylhydrocarbyl radicals), said Q having up to        20 carbons with the proviso that in not more than one occurrence        is Q halide. Examples of suitable hydrocarbyloxide Q groups are        disclosed in U.S. Pat. No. 5,296,433, the entire disclosure of        which is hereby incorporated herein by reference.

In a more preferred embodiment, d is one, that is, the counter ion has asingle negative charge and is A⁻. Activating cocatalysts comprisingboron which are particularly useful in the preparation of the catalystsherein may be represented by the following general formula:(L*-H)⁺(BQ₄)⁻

-   -   wherein L* is as previously defined;    -   B is boron in a formal oxidation state of 3; and    -   Q is a hydrocarbyl-, hydrocarbyloxy-, fluorinated hydrocarbyl-,        fluorinated hydrocarbyloxy-, or fluorinated        silylhydrocarbyl-group of up to 20 nonhydrogen atoms, with the        proviso that in not more than one occasion is Q hydrocarbyl.

Preferred Lewis base salts are ammonium salts, more preferablytrialkylammonium salts containing one or more C₁₂-C₄₀ alkyl groups. Mostpreferably, Q is each occurrence a fluorinated aryl group, especially apentafluorophenyl group.

Preferred (L*-H)⁺ cations are methyldioctadecylammonium cations,dimethyloctadecylammonium cations, and ammonium cations derived frommixtures of trialkyl amines containing one or two C₁₄-C₁₈ alkyl groups.

Another suitable ion forming, activating cocatalyst comprises a salt ofa cationic oxidizing agent and a noncoordinating, compatible anionrepresented by the formula:(Ox^(h+))_(g)(A^(g−))_(h),

-   -   wherein Ox^(h+) is a cationic oxidizing agent having a charge of        h+;    -   h is an integer from 1 to 3; and    -   A^(g−) and g are as previously defined.    -   Examples of cationic oxidizing agents include: ferrocenium,        hydrocarbyl-substituted ferrocenium, Ag⁺ or Pb⁺². Preferred        embodiments of A^(g−) are those anions previously defined with        respect to the Bronsted acid containing activating cocatalysts,        especially tetrakis(pentafluorophenyl)borate.

Another suitable ion forming, activating cocatalyst comprises a compoundwhich is a salt of a carbenium ion and a non-coordinating, compatibleanion represented by the formula:[C]⁺A⁻

-   -   wherein [C]⁺ is a C₁-C₂₀ carbenium ion; and    -   A⁻ is a noncoordinating, compatible anion having a charge of −1.        A preferred carbenium ion is the trityl cation, that is        triphenylmethylium.

A further suitable ion forming, activating cocatalyst comprises acompound which is a salt of a silylium ion and a noncoordinating,compatible anion represented by the formula:(Q¹ ₃Si)⁺A⁻

-   -   wherein Q¹ is C₁-C₁₀ hydrocarbyl, and A⁻ is as previously        defined.

Preferred silylium salt activating cocatalysts are trimethylsilyliumtetrakispentafluorophenylborate, triethylsilyliumtetrakispentafluorophenylborate and ether substituted adducts thereof.Silylium salts have been previously generically disclosed in J. ChemSoc. Chem. Comm., 1993, 383-384, as well as Lambert, J. B., et al.,Organometallics, 1994, 13, 2430-2443, the disclosures of which arehereby incorporated herein by reference. The use of the above silyliumsalts as activating cocatalysts for addition polymerization catalysts isdisclosed in U.S. Pat. No. 5,625,087, the entire disclosure of which ishereby incorporated herein by reference.

Certain complexes of alcohols, mercaptans, silanols, and oximes withtris(pentafluorophenyl)borane are also effective catalyst activators andmay be used according to the present invention. Such cocatalysts aredisclosed in U.S. Pat. No. 5,296,433, the entire disclosure of which ishereby incorporated herein by reference.

Suitable activating cocatalysts for use herein also include polymeric oroligomeric alumoxanes, especially methylalumoxane (MAO), triisobutylaluminum modified methylalumoxane (MMAO), or isobutylalumoxane; Lewisacid modified alumoxanes, especially perhalogenatedtri(hydrocarbyl)aluminum- or perhalogenated tri(hydrocarbyl)boronmodified alumoxanes, having from 1 to 10 carbons in each hydrocarbyl orhalogenated hydrocarbyl group, and most especiallytris(pentafluorophenyl)borane modified alumoxanes. Such cocatalysts arepreviously disclosed, for example, in U.S. Pat. Nos. 6,214,760,6,160,146, 6,140,521, and 6,696,379, the entire disclosures of which arehereby incorporated herein by reference.

A class of cocatalysts comprising non-coordinating anions genericallyreferred to as expanded anions, further disclosed in U.S. Pat. No.6,395,671, the entire disclosure of which is hereby incorporated hereinby reference, may be suitably employed to activate the metal complexesof the present invention for olefin polymerization. Generally, thesecocatalysts (illustrated by those having imidazolide, substitutedimidazolide, imidazolinide, substituted imidazolinide, benzimidazolide,or substituted benzimidazolide anions) may be depicted as follows:

-   -   wherein A*⁺ is a cation, especially a proton containing cation,        and preferably is a trihydrocarbyl ammonium cation containing        one or two C₁₀-C₄₀ alkyl groups, especially a methyldi(C₁₄-C₂₀        alkyl)ammonium cation,    -   Q³, independently each occurrence, is hydrogen or a halo,        hydrocarbyl, halocarbyl, halohydrocarbyl, silylhydrocarbyl, or        silyl, (including mono-, di- and tri-(hydrocarbyl)silyl) group        of up to 30 atoms not counting hydrogen, preferably C₁-C₂₀        alkyl, and    -   Q² is tris(pentafluorophenyl)borane or        tris(pentafluorophenyl)alumane.

Other activators include those described in PCT Publication Nos.WO98/07515, the entire disclosure of which is hereby incorporated hereinby reference, such as tris(2,2′, 2″-nonafluorobiphenyl)fluoroaluminate.Combinations of activators are also contemplated by the invention, forexample, alumoxanes and ionizing activators in combinations, see forexample, European Publication EP-A-0573120, PCT Publication Nos.WO94/07928 and WO95/14044, and U.S. Pat. Nos. 5,153,157 and 5,453,410,the entire disclosures of which are hereby incorporated herein byreference. WO98/09996 describes activating catalyst compounds withperchlorates, periodates and iodates, including their hydrates.WO99/18135 describes the use of organoboroaluminum activators.WO03/10171 discloses catalyst activators that are adducts of Bronstedacids with Lewis acids. Each of these references is hereby incorporatedherein by reference in its entirety. Other activators or methods foractivating a catalyst compound are described in, for example, U.S. Pat.Nos. 5,849,852, 5,859,653, 5,869,723, European Publication EP-A-615981,and PCT Publication No. WO98/32775, the entire disclosures of which arehereby incorporated herein by reference. All of the foregoing catalystactivators as well as any other known activator for transition metalcomplex catalysts may be employed alone or in combination according tothe present invention, however, for best results alumoxane containingcocatalysts are avoided.

The molar ratio of catalyst/cocatalyst employed preferably ranges from1:10,000 to 100:1, more preferably from 1:5000 to 10:1, most preferablyfrom 1:1000 to 1:1. Alumoxane, when used by itself as an activatingcocatalyst, is employed in large quantity, generally at least 100 timesthe quantity of metal complex on a molar basis.Trispentafluorophenyl)borane, where used as an activating cocatalyst isemployed in a molar ratio to the metal complex of from 0.5:1 to 10:1,more preferably from 1:1 to 6:1, most preferably from 1:1 to 5:1. Theremaining activating cocatalysts are generally employed in approximatelyequimolar quantity with the metal complex.

Suitable catalyst activators are further disclosed in PCT PublicationNos. WO2005/090425, WO2005/090426, and WO2005/090427, the entiredisclosures of which are hereby incorporated herein by reference.

In the process of the invention, an activated catalyst site A, underpolymerization conditions, forms a polymer chain attached to activecatalyst site A. Similarly, active catalyst site B produces adifferentiated polymer chain attached to active catalyst site B. A chainshuttling agent C1, attached to a polymer chain produced by activecatalyst B, exchanges its polymer chain for the polymer chain attachedto catalyst site A. Additional chain growth under polymerizationconditions causes formation of a multi-block copolymer attached toactive catalyst site A. Similarly, chain shuttling agent C2, attached toa polymer chain produced by active catalyst site A, exchanges itspolymer chain for the polymer chain attached to catalyst site B.Additional chain growth under polymerization conditions causes formationof a multi-block copolymer attached to active catalyst site B. Thegrowing multi-block copolymers are repeatedly exchanged between activecatalyst A and active catalyst B by means of a shuttling agent Cresulting in formation of a block or segment of differing propertieswhenever exchange to the opposite active catalyst site occurs. Thegrowing polymer chains may be recovered while attached to a chainshuttling agent and functionalized if desired. Alternatively, theresulting polymer may be recovered by scission from the active catalystsite or the shuttling agent, through use of a proton source or otherkilling agent.

It is believed, without wishing to be bound by such belief, that thecomposition of the respective segments or blocks, and especially of theend segments of the polymer chains, may be influenced through selectionof process conditions or other process variables. In the polymers of theinvention, the nature of the end segments is determined by the relativerates of chain transfer or termination for the respective catalysts aswell as by the relative rates of chain shuttling. Possible chaintermination mechanisms include, but are not limited to, β-hydrogenelimination, β-hydrogen transfer to monomer, β-methyl elimination, andchain transfer to hydrogen or other chain-terminating reagent such asorganosilane or chain functionalizing agent. Accordingly, when a lowconcentration of chain shuttling agent is used, the majority of polymerchain ends will be generated in the polymerization reactor by one of theforegoing chain termination mechanisms and the relative rates of chaintermination for catalyst (A) and (B) will determine the predominantchain terminating moiety. That is, the catalyst having the fastest rateof chain termination will produce relatively more chain end segments inthe finished polymer.

In contrast, when a high concentration of chain shuttling agent isemployed, the majority of the polymer chains within the reactor and uponexiting the polymerization zone are attached or bound to the chainshuttling agent. Under these reaction conditions, the relative rates ofchain transfer of the polymerization catalysts and the relative rate ofchain shuttling of the two catalysts primarily determines the identityof the chain terminating moiety. If catalyst (A) has a faster chaintransfer and/or chain shuttling rate than catalyst (B), then themajority of the chain end segments will be those produced by catalyst(A).

At intermediate concentrations of chain shuttling agent, all three ofthe aforementioned factors are instrumental in determining the identityof the final polymer block. The foregoing methodology may be expanded tothe analysis of multi-block polymers having more than two block typesand for controlling the average block lengths and block sequences forthese polymers. For example, using a mixture of catalysts 1, 2, and 3with a chain shuttling agent, for which each catalyst type makes adifferent type of polymer block, produces a linear block copolymer withthree different block types. Furthermore, if the ratio of the shuttlingrate to the propagation rate for the three catalysts follows the order1>2>3, then the average block length for the three block types willfollow the order 3>2>1, and there will be fewer instances of 2-typeblocks adjacent to 3-type blocks than 1-type blocks adjacent to 2-typeblocks.

It follows that a method exists for controlling the block lengthdistribution of the various block types. For example, by selectingcatalysts 1, 2, and 3 (wherein 2 and 3 produce substantially the samepolymer block type), and a chain shuttling agent, and the shuttling ratefollows the order 1>2>3, the resulting polymer will have a bimodaldistribution of block lengths made from the 2 and 3 catalysts.

During the polymerization, the reaction mixture comprising the monomeror monomers to be polymerized is contacted with the activated catalystcomposition according to any suitable polymerization conditions. Theprocess is characterized by use of elevated temperatures and pressures.Hydrogen may be employed as a chain transfer agent for molecular weightcontrol according to known techniques if desired. As in other similarpolymerizations, it is highly desirable that the monomers and solventsemployed be of sufficiently high purity that catalyst deactivation doesnot occur. Any suitable technique for monomer purification such asdevolatilization at reduced pressure, contacting with molecular sievesor high surface area alumina, or a combination of the foregoingprocesses may be employed. The skilled artisan will appreciate that theratio of chain shuttling agent to one or more catalysts and or monomersin the process of the present invention may be varied in order toproduce polymers differing in one or more chemical or physicalproperties.

Supports may be employed in the present invention, especially in slurryor gas-phase polymerizations. Suitable supports include solid,particulated, high surface area, metal oxides, metalloid oxides, ormixtures thereof (interchangeably referred to herein as an inorganicoxide). Examples include: talc, silica, alumina, magnesia, titania,zirconia, Sn₂O₃, aluminosilicates, borosilicates, clays, and mixturesthereof. Suitable supports preferably have a surface area as determinedby nitrogen porosimetry using the B.E.T. method from 10 to 1000 m²/g,and preferably from 100 to 600 m²/g. The average particle size typicallyis from 0.1 to 500 μm, preferably from 1 to 200 μm, and more preferablyfrom 10 to 100 μm.

In one embodiment of the invention the present catalyst composition andoptional support may be spray dried or otherwise recovered in solid,particulated form to provide a composition that is readily transportedand handled. Suitable methods for spray drying a liquid containingslurry are well known in the art and usefully employed herein. Preferredtechniques for spray drying catalyst compositions for use herein aredescribed in U.S. Pat. Nos. 5,648,310 and 5,672,669, the entiredisclosures of which are hereby incorporated herein by reference.

The polymerization is desirably carried out as a continuouspolymerization, preferably a continuous solution polymerization, inwhich catalyst components, shuttling agent(s), monomers, and optionallysolvent, adjuvants, scavengers, and polymerization aids are continuouslysupplied to the reaction zone and polymer product continuously removedthere from. Within the scope of the terms “continuous” and“continuously” as used in this context are those processes in whichthere are intermittent additions of reactants and removal of products atsmall regular or irregular intervals, so that, over time, the overallprocess is substantially continuous.

The catalyst compositions can be advantageously employed in a highpressure, solution, slurry, or gas phase polymerization process. For asolution polymerization process it is desirable to employ homogeneousdispersions of the catalyst components in a liquid diluent in which thepolymer is soluble under the polymerization conditions employed. Onesuch process utilizing an extremely fine silica or similar dispersingagent to produce such a homogeneous catalyst dispersion where either themetal complex or the cocatalyst is only poorly soluble is disclosed inU.S. Pat. No. 5,783,512, the entire disclosure of which is herebyincorporated herein by reference. A solution process to prepare thepolymers of the present invention, especially a continuous solutionprocess is preferably carried out at a temperature between 80° C. and250° C., more preferably between 100° C. and 210° C., and mostpreferably between 110° C. and 210° C. A high pressure process isusually carried out at temperatures from 100° C. to 400° C. and atpressures above 500 bar (50 MPa). A slurry process typically uses aninert hydrocarbon diluent and temperatures of from 0° C. up to atemperature just below the temperature at which the resulting polymerbecomes substantially soluble in the inert polymerization medium.Preferred temperatures in a slurry polymerization are from 30° C.,preferably from 60° C. up to 115° C., preferably up to 100° C. Pressurestypically range from atmosphelic (100 kPa) to 500 psi (3.4 MPa).

In all of the foregoing processes, continuous or substantiallycontinuous polymerization conditions are preferably employed. The use ofsuch polymerization conditions, especially continuous, solutionpolymerization processes employing two or more active polymerizationcatalyst species, allows the use of elevated reactor temperatures whichresults in the economical production of multi-block copolymers in highyields and efficiencies. Both homogeneous and plug-flow type reactionconditions may be employed. The latter conditions are preferred wheretapering of the block composition is desired.

Both catalyst composition (A) and (B) may be prepared as a homogeneouscomposition by addition of the requisite metal complexes to a solvent inwhich the polymerization will be conducted or in a diluent compatiblewith the ultimate reaction mixture. The desired cocatalyst or activatorand the shuttling agent may be combined with the catalyst compositioneither prior to, simultaneously with, or after combination with themonomers to be polymerized and any additional reaction diluent.

At all times, the individual ingredients as well as any active catalystcomposition must be protected from oxygen and moisture. Therefore, thecatalyst components, shuttling agent and activated catalysts must beprepared and stored in an oxygen and moisture free atmosphere,preferably a dry, inert gas such as nitrogen.

Without limiting in any way the scope of the invention, one means forcarrying out such a polymerization process is as follows. In astirred-tank reactor, the monomers to be polymerized are introducedcontinuously together with any solvent or diluent. The reactor containsa liquid phase composed substantially of monomers together with anysolvent or diluent and dissolved polymer. Preferred solvents includeC₄-C₁₀ hydrocarbons or mixtures thereof, especially alkanes such ashexane or mixtures of alkanes, as well as one or more of the monomersemployed in the polymerization.

Two or more catalysts along with cocatalyst and chain shuttling agentare continuously or intermittently introduced in the reactor liquidphase or any recycled portion thereof. The reactor temperature andpressure may be controlled by adjusting the solvent/monomer ratio, thecatalyst addition rate, as well as by cooling or heating coils, jacketsor both. The polymerization rate is controlled by the rate of catalystaddition. The comonomer content of the polymer product is determined bythe ratio of major monomer to comonomer in the reactor, which iscontrolled by manipulating the respective feed rates of these componentsto the reactor. The polymer product molecular weight is controlled,optionally, by controlling other polymerization variables such as thetemperature, monomer concentration, or by the previously mentioned chaintransfer agent, as is well known in the art. Upon exiting the reactor,the effluent is contacted with a catalyst kill agent such as water,steam, or an alcohol. The polymer solution is optionally heated, and thepolymer product is recovered by flashing off gaseous monomers as well asresidual solvent or diluent at reduced pressure, and, if necessary,conducting further devolatilization in equipment such as adevolatilizing extruder. In a continuous process the mean residence timeof the catalyst and polymer in the reactor generally is from 5 minutesto 8 hours, and preferably from 10 minutes to 6 hours.

Alternatively, the foregoing polymerization may be carried out in acontinuous loop reactor with or without a monomer, catalyst or shuttlingagent gradient established between differing regions thereof, optionallyaccompanied by separated addition of catalysts and/or chain transferagent, and operating under adiabatic or non-adiabatic solutionpolymerization conditions or combinations of the foregoing reactorconditions. Examples of suitable loop reactors and a variety of suitableoperating conditions for use therewith are found in U.S. Pat. Nos.5,977,251, 6,319,989, and 6,683,149, the entire disclosures of which arehereby incorporated herein by reference.

Although not as desired, the catalyst composition may also be preparedand employed as a heterogeneous catalyst by adsorbing the requisitecomponents on an inert inorganic or organic particulated solid, aspreviously disclosed. In a preferred embodiment, a heterogeneouscatalyst is prepared by co-precipitating the metal complex and thereaction product of an inert inorganic compound and an active hydrogencontaining activator, especially the reaction product of a tri(C₁-C₄alkyl) aluminum compound and an ammonium salt of ahydroxyaryltris(pentafluorophenyl)borate, such as an ammonium salt of(4-hydroxy-3,5-ditertiarybutylphenyl)tris(pentafluorophenyl)borate. Whenprepared in heterogeneous or supported form, the catalyst compositionmay be employed in a slurry or a gas phase polymerization. As apractical limitation, slurry polymerization takes place in liquiddiluents in which the polymer product is substantially insoluble.Preferably, the diluent for slurry polymerization is one or morehydrocarbons with less than 5 carbon atoms. If desired, saturatedhydrocarbons such as ethane, propane or butene may be used in whole orpart as the diluent. As with a solution polymerization, the monomer or amixture of different monomers may be used in whole or part as thediluent. Most preferably at least a major part of the diluent comprisesthe monomers to be polymerized.

Preferably for use in gas phase polymerization processes, the supportmaterial and resulting catalyst has a median particle diameter from 20to 200 μm, more preferably from 30 μm to 150 μm, and most preferablyfrom 50 μm to 100 μm. Preferably for use in slurry polymerizationprocesses, the support has a median particle diameter from 1 μm to 200μm, more preferably from 5 μm to 100 μm, and most preferably from 10 μmto 80 μm.

Suitable gas phase polymerization processes for use herein aresubstantially similar to known processes used commercially on a largescale for the manufacture of polypropylene, ethylene/α-olefincopolymers, and other olefin polymers. The gas phase process employedcan be, for example, of the type which employs a mechanically stirredbed or a gas fluidized bed as the polymerization reaction zone.Preferred is the process wherein the polymerization reaction is carriedout in a vertical cylindrical polymerization reactor containing afluidized bed of polymer particles supported or suspended above aperforated plate or fluidization grid, by a flow of fluidization gas.

The gas employed to fluidize the bed comprises the monomer or monomersto be polymerized, and also serves as a heat exchange medium to removethe heat of the reaction from the bed. The hot gases emerge from the topof the reactor, normally via a tranquilization zone, also known as avelocity reduction zone, having a wider diameter than the fluidized bedand wherein fine particles entrained in the gas stream have anopportunity to gravitate back into the bed. It can also be advantageousto use a cyclone to remove ultra-fine particles from the hot gas stream.The gas is then normally recycled to the bed by means of a blower orcompressor and one or more heat exchangers to strip the gas of the heatof polymerization.

A preferred method of cooling of the bed, in addition to the coolingprovided by the cooled recycle gas, is to feed a volatile liquid to thebed to provide an evaporative cooling effect, often referred to asoperation in the condensing mode. The volatile liquid employed in thiscase can be, for example, a volatile inert liquid, for example, asaturated hydrocarbon having 3 to 8, preferably 4 to 6, carbon atoms. Inthe case that the monomer or comonomer itself is a volatile liquid, orcan be condensed to provide such a liquid, this can suitably be fed tothe bed to provide an evaporative cooling effect. The volatile liquidevaporates in the hot fluidized bed to form gas which mixes with thefluidizing gas. If the volatile liquid is a monomer or comonomer, itwill undergo some polymerization in the bed. The evaporated liquid thenemerges from the reactor as part of the hot recycle gas, and enters thecompression/heat exchange part of the recycle loop. The recycle gas iscooled in the heat exchanger and, if the temperature to which the gas iscooled is below the dew point, liquid will precipitate from the gas.This liquid is desirably recycled continuously to the fluidized bed. Itis possible to recycle the precipitated liquid to the bed as liquiddroplets carried in the recycle gas stream. This type of process isdescribed, for example in European Publication EP-89691, U.S. Pat. No.4,543,399, PCT Publication No. WO94/25495, and U.S. Pat. No. 5,352,749.A particularly preferred method of recycling the liquid to the bed is toseparate the liquid from the recycle gas stream and to reinject thisliquid directly into the bed, preferably using a method which generatesfine droplets of the liquid within the bed. This type of process isdescribed in PCT Publication No. WO94/28032.

The polymerization reaction occurring in the gas fluidized bed iscatalyzed by the continuous or semi-continuous addition catalystcomposition according to the invention. The catalyst composition may besubjected to a prepolymerization step, for example, by polymerizing asmall quantity of olefin monomer in a liquid inert diluent, to provide acatalyst composite comprising supported catalyst particles embedded inolefin polymer particles as well.

The polymer is produced directly in the fluidized bed by polymerizationof the monomer or mixture of monomers on the fluidized particles ofcatalyst composition, supported catalyst composition or prepolymerizedcatalyst composition within the bed. Start-up of the polymerizationreaction is achieved using a bed of preformed polymer particles, whichare preferably similar to the desired polymer, and conditioning the bedby drying with inert gas or nitrogen prior to introducing the catalystcomposition, the monomers and any other gases which it is desired tohave in the recycle gas stream, such as a diluent gas, hydrogen chaintransfer agent, or an inert condensable gas when operating in gas phasecondensing mode. The produced polymer is discharged continuously orsemi-continuously from the fluidized bed as desired.

The gas phase processes most suitable for the practice of this inventionare continuous processes which provide for the continuous supply ofreactants to the reaction zone of the reactor and the removal ofproducts from the reaction zone of the reactor, thereby providing asteady-state environment on the macro scale in the reaction zone of thereactor. Products are readily recovered by exposure to reduced pressureand optionally elevated temperatures (devolatilization) according toknown techniques. Typically, the fluidized bed of the gas phase processis operated at temperatures greater than 50° C., preferably from 60° C.to 100° C., more preferably from 70° C. to 110° C.

Examples of gas phase processes which are adaptable for use in theprocess of this invention are disclosed in U.S. Pat. Nos. 4,588,790,4,543,399, 5,352,749, 5,436,304, 5,405,922, 5,462,999, 5,461,123,5,453,471, 5,032,562, 5,028,670, 5,473,028, 5,106,804, 5,556,238,5,541,270, 5,608,019, and 5,616,661.

As previously mentioned, functionalized derivatives of multi-blockcopolymers are also included within the present invention. Examplesinclude metallated polymers wherein the metal is the remnant of thecatalyst or chain shuttling agent employed, as well as furtherderivatives thereof, for example, the reaction product of a metallatedpolymer with an oxygen source and then with water to form a hydroxylterminated polymer. In another embodiment, sufficient air or otherquench agent is added to cleave some or all of the shuttlingagent-polymer bonds thereby converting at least a portion of the polymerto a hydroxyl terminated polymer. Additional examples include olefinterminated polymers formed by β-hydride elimination and ethylenicunsaturation in the resulting polymer.

In one embodiment, the multi-block copolymer may be functionalized bymaleation (reaction with maleic anhydride or its equivalent),metallation (such as with an alkyl lithium reagent, optionally in thepresent of a Lewis base, especially an amine, such astetramethylethylenediamine), or by incorporation of a diene or maskedolefin in a copolymerization process. After polymerization involving amasked olefin, the masking group, for example a trihydrocarbylsilane,may be removed thereby exposing a more readily functionalized remnant.Techniques for functionalization of polymers are well known, anddisclosed for example in U.S. Pat. No. 5,543,458, and elsewhere.

Because a substantial fraction of the polymeric product exiting thereactor is terminated with the chain shuttling agent, furtherfunctionalization is relatively easy. The metallated polymer species canbe utilized in well known chemical reactions such as those suitable forother alkyl-aluminum, alkyl-gallium, alkyl-zinc, or alkyl-Group 1compounds to form amine-, hydroxy-, epoxy-, ketone-, ester-, nitrile-,and other functionalized terminated polymer products. Examples ofsuitable reaction techniques that are adaptable for use herein aredescribe in Negishi, “Organometallics in Organic Synthesis,” Vol. 1 and2, (1980), and other standard texts in organometallic and organicsynthesis.

Polymer Products

Utilizing the present process, novel polymers, including multi-blockcopolymers, are readily prepared.

In one embodiment, the polymers preferably comprise in polymerized form,ethylene having blocks of segments characterized by the presence ofhyper-branching and other segments of highly crystalline polyethylene.The multi-block copolymers of this embodiment are believed to becharacterized by the presence of differentiated blocks within thepolymer chains, having both crystalline and amorphous nature. Thepresence of such differentiated blocks in the polymers can be identifiedby unique TREF elution curves as well as ATREFF or other standardanalytical techniques. The multi-block polymers of this embodimentpreferably possess a heat of fusion of 130 J/g or less, an ethylenecontent (that is —CH₂—CH₂ polymer segments) of at least 50 weightpercent, preferably at least 90 percent, a glass transition temperature,T_(g), of less than −25° C., more preferably less than −30° C., and/orone and only one T_(m). Additionally, the polymers of the invention canhave a melt index, I₂, from 0.01 to 2000 g/10 minutes, preferably from0.01 to 1000 g/10 minutes, more preferably from 0.01 to 500 g/10minutes, and especially from 0.01 to 100 g/10 minutes. Desirably, thepolymers of the invention can have molecular weights, M_(w), from 1,000g/mole to 5,000,000 g/mole, preferably from 1000 g/mole to 1,000,000,more preferably from 10000 g/mole to 500,000 g/mole, and especially from10,000 g/mole to 300,000 g/mole. The density of the polymers of theinvention can be from 0.80 to 0.99 g/cm³ and preferably for ethylenecontaining polymers from 0.85 g/cm³ to 0.97 g/cm³. Polymers of thisembodiment are further disclosed in PCT Publication No. WO2005/090425,the entire disclosure of which is hereby incorporated herein byreference.

In another embodiment, the polymers prepared by the present process aremulti-block copolymers of propylene or 4-methyl-1-pentene and one ormore comonomers. Preferably, the polymers comprise in polymerized form,propylene and ethylene and/or one or more C₄-C₂₀ α-olefin comonomers,and/or one or more additional copolymerizable comonomers or theycomprise 4-methyl-1-pentene and ethylene and/or one or more C₄-C₂₀α-olefin comonomers, and/or one or more additional copolymerizablecomonomers. Preferred α-olefins are C₄-C₈ α-olefins. Suitable comonomersare selected from diolefins, cyclic olefins, and cyclic diolefins,halogenated vinyl compounds, and vinylidene aromatic compounds.Comonomer content in the resulting interpolymers may be measured usingany suitable technique, with techniques based on nuclear magneticresonance (NMR) spectroscopy preferred. It is highly desirable that someor all of the polymer blocks comprise amorphous or relatively amorphouspolymers such as copolymers of propylene or 4-methyl-1-pentene and acomonomer, especially random copolymers of propylene or4-methyl-1-pentene with ethylene, and any remaining polymer blocks (hardsegments), if any, predominantly comprise propylene or4-methyl-1-pentene in polymerized form. Preferably such segments arehighly crystalline or stereospecific polypropylene orpoly-4-methyl-1-pentene, especially isotactic homopolymers, containingat least 99 mole percent propylene or 4-methyl-1-pentene therein.Further preferably, the interpolymers comprise from 10 to 90 percentcrystalline or relatively hard segments and 90 to 10 percent amorphousor relatively amorphous segments (soft segments). Within the softsegments, the mole percent propylene, 4-methyl-1-pentene, or otherα-olefin may range from 1 to 85 percent, preferably from 5 to 50 molepercent. Alternatively, the soft segments may result from polymerizationof a single monomer (or more than one monomer), especially ethylenealone, under conditions leading to formation of branching, 1,3-monomeraddition sequences, or long chain branching as a result of chain walkingor other branch forming process. The polymers may be differentiated fromconventional, random copolymer, physical blends of polymers, and blockcopolymers prepared via sequential monomer addition, fluxionalcatalysts, anionic or cationic living polymerization techniques. Inparticular, compared to a random copolymer of the same monomers andmonomer content at equivalent crystallinity or modulus, the polymers ofthe invention have better (higher) heat resistance as measured bymelting point, higher TMA penetration temperature, higherhigh-temperature tensile strength, and/or higher high-temperaturetorsion modulus as determined by dynamic mechanical analysis. Comparedto a random copolymer comprising the same monomers and monomer content,polymers of the invention may have one or more of the following: lowercompression set, particularly at elevated temperatures, lower stressrelaxation, higher creep resistance, higher tear strength, higherblocking resistance, faster setup due to higher crystallization(solidification) temperature, higher recovery (particularly at elevatedtemperatures), better abrasion resistance, higher retractive force, andbetter oil and filler acceptance. Further preferably, the polymers ofthis embodiment have an ethylene content of from 60 to 90 percent, adiene content of from 0.1 to 10 percent, and a propylene and/or α-olefincontent of from 10 to 40 percent, based on the total weight of thepolymer. Preferred polymers are high molecular weight polymers, having aweight average molecular weight (M_(w)) of from 10,000 to 2,500,000 anda polydispersity of less than 3.5, more preferably less than 3.0. Morepreferably, such polymers have an ethylene content of from 65 to 75percent, a diene content of from 0 to 6 percent, a propylene and/orα-olefin content of from 20 to 35 percent, a M_(w) of from 20,000 to250,000 and a polydispersity of from 1.5 to 3.0. Polymers of thisembodiment are further disclosed in PCT Publication No. WO2005/090426,the entire disclosure of which is hereby incorporated herein byreference.

In another embodiment, the polymers preferably comprise in polymerizedform ethylene and at least one C₃-C₂₀ α-olefin comonomer, and optionallyone or more additional copolymerizable comonomers. Preferred α-olefinsare C₃-C₈ α-olefins. Suitable comonomers are selected from diolefins,cyclic olefins, and cyclic diolefins, halogenated vinyl compounds, andvinylidene aromatic compounds. In a first particular aspect of thisembodiment, the polymer has at least one melting point, T_(m), indegrees Celsius and density, d*, in grams/cubic centimeter, wherein thenumerical values of the variables correspond to the relationship:T_(m)>−2002.9+4538.5(d*)−2422.2(d*)²and wherein the polymer has a M_(w)/M_(n) of from 1.7 to 3.5. In asecond particular aspect of this embodiment, the polymer has at leastone melting point, T_(m), in degrees Celsius and density, d*, ingrams/cubic centimeter, wherein the numerical values of the variablescorrespond to the relationship:T_(m)>−6288.1+13141(d*)−6720.3(d*)².In a third particular aspect of this embodiment, the polymer has atleast one melting point, T_(m), in degrees Celsius and density, d*, ingrams/cubic centimeter, wherein the numerical values of the variablescorrespond to the relationship:T_(m)≧858.91−1825.3(d*)+1112.8(d*)².In a fourth particular aspect of this embodiment, the polymer comprisesin polymerized form ethylene and a C₃-C₈ α-olefin, said polymer having adelta quantity (tallest DSC peak minus tallest CRYSTAF peak) greaterthan the quantity, y*, defined by the equation:y*>−0.1299(ΔH)+62.81,preferably the equation:y*>−0.1299(ΔH)+64.38,and more preferably the equation:y*>−0.1299(ΔH)+65.95,at a heat of fusion up to 130 J/g, wherein the CRYSTAF peak isdetermined using at least 5 percent of the cumulative polymer (that is,the peak must represent at least 5 percent of the cumulative polymer),and if less than 5 percent of the polymer has an identifiable CRYSTAFpeak, then the CRYSTAF temperature is 30° C., and AH is the numericalvalue of the heat of fusion in J/g. More preferably, the highest CRYSTAFpeak comprises at least 10 percent of the cumulative polymer. In a fifthparticular aspect of this embodiment, the polymer has a tensile strengthabove 10 MPa, preferably a tensile strength ≧11 MPa, more preferably atensile strength ≧13 MPa and an elongation at break of at least 600percent, more preferably at least 700 percent, highly preferably atleast 800 percent, and most highly preferably at least 900 percent at acrosshead separation rate of 11 cm/minute. In a sixth particular aspectof this embodiment, the polymer has a delta quantity (tallest DSC peaktemperature (measured from the baseline) minus tallest CRYSTAF peaktemperature (i.e., highest numerical value of dW/dT)) greater than 48°C. and a heat of fusion greater than or equal to 130 J/gm, wherein theCRYSTAF peak is determined using at least 5 percent of the cumulativepolymer (that is, the peak must represent at least 5 percent of thecumulative polymer), and if less than 5 percent of the polymer has anidentifiable CRYSTAF peak, then the CRYSTAF temperature is 30° C. Morepreferably, the highest CRYSTAF peak comprises at least 10 percent ofthe cumulative polymer. In a seventh particular aspect of thisembodiment, the polymer has a storage modulus ratio, G′(25° C.)/G′(100°C.), of from 1 to 50, preferably from 1 to 20, more preferably from 1 to10, and a 70° C. compression set of less than 80 percent, preferablyless than 70 percent, especially less than 60 percent, down to acompression set of 0 percent. In an eighth particular aspect of thisembodiment, the polymer has a heat of fusion of less than 85 J/g and apellet blocking strength of equal to or less than 100 pounds/foot² (4800MPa), preferably equal to or less than 50 lbs/ft² (2400 MPa), especiallyequal to or less than 5 lbs/ft² (240 Pa), and as low as 0 lbs/ft². In aninth particular aspect of this embodiment, the polymer is anuncrosslinked, elastomeric interpolymer comprising in polymerized format least 50 mole percent ethylene, having a 70° C. compression set ofless than 80 percent, preferably less than 70 percent, most preferablyless than 60 percent. In a tenth particular aspect of this embodiment,the polymer is an olefin interpolymer, preferably comprising ethyleneand one or more copolymerizable comonomers in polymerized form,characterized by multiple blocks or segments of two or more polymerizedmonomer units differing in chemical or physical properties (blockedinterpolymer), most preferably a multi-block copolymer, said blockinterpolymer having a molecular fraction which elutes between 40° C. and130° C. when fractionated using TREF, characterized in that saidfraction has a molar comonomer content higher, preferably at least 5percent higher, more preferably at least 10 percent higher, than that ofa comparable random ethylene interpolymer fraction eluting between thesame temperatures, wherein said comparable random ethylene interpolymercomprises the same comonomer(s), and has a melt index, density, andmolar comonomer content (based on the whole polymer) within 10 percentof that of the blocked interpolymer. Preferably, the M_(w)/M_(n) of thecomparable interpolymer is also within 10 percent of that of the blockedinterpolymer and/or the comparable interpolymer has a total comonomercontent within 10 weight percent of that of the blocked interpolymer.Polymers of this embodiment preferably have an ethylene content of from20 to 90 percent, a diene content of from 0.1 to 10 percent, and anα-olefin content of from 10 to 80 percent, based on the total weight ofthe polymer. Further preferably, the polymers of this embodiment have anethylene content of from 60 to 90 percent, a diene content of from 0.1to 10 percent, and an α-olefin content of from 10 to 40 percent, basedon the total weight of the polymer. Even more preferably, the polymersof this embodiment have an ethylene content of from 65 to 75 percent, adiene content of from 0 to 6 percent, and an α-olefin content of from 20to 35 percent. Preferred polymers are high molecular weight polymers,having a weight average molecular weight (M_(w)) of from 10,000 to2,500,000, preferably from 20,000 to 500,000, more preferably from20,000 to 350,000, and a polydispersity of less than 3.5, morepreferably less than 3.0, and a Mooney viscosity (ML (1+4) 125° C.) offrom 1 to 250. Polymers of this embodiment are further disclosed in PCTPublication No. WO2005/090427, the entire disclosure of which is herebyincorporated herein by reference. Particularly preferred polymers ofthis embodiment include the ethylene-octene multi-block copolymers givenin Table 1 below.

TABLE 1 Example No. 1 2 3 4 5 6 7 8* Hard Segment (wt %) 0 12 31 61 7184 100 — I₂ (g/10 min) 1.2 1.7 1.4 1.0 1.1 1.0 4.9 1.0 M_(w) (kg/mol)129 112 124 108 100 102 76 — M_(w)/M_(n) 2.1 2.0 2.1 1.9 1.9 1.9 1.9 —Density, ρ (g/cm³) 0.8582 0.8649 0.8795 0.9022 0.9097 0.9202 0.94190.8724 Density, X_(c) (wt %) 3 8 19 36 41 49 64 14 DMTA, T_(g) (° C.)−44 −43 −42 −34 −31 −19 — — ΔH_(m) (J/g) 5 19 49 89 115 137 178 45 DSC,X_(c) (wt %) 2 7 17 31 40 47 61 15 X-ray, X_(c) (wt %) — 6 19 35 41 50 —— σ_(y) (MPa) 00.9 01.2 02.5 07.3 10.4 13.7 23.4 02.2 E at 5% (MPa) 3 617 72 98 166 359 10 Recovery from 300% 95 94 85 62 47 28 14 71 Strain at10 min (%) *Example No. 8 is a commercial elastomeric homogeneousethylene-octene copolymer shown for comparative purposes.

Polymers having the properties given in Table 1 are further disclosed,for example, in the technical paper “Solid State Structure andProperties of Novel Olefin Block Copolymer,” Hiltner, A., et al., firstpresented at ANTEC 2006, SPE's Annual Technical Conference, May 7-11,2006, Charlotte, N.C. The publication is currently available athttp://www.dow.con/PublishedLiterature/dh_(—)057c/09002f138057c984.pdf.?filepath=infuse/pdfs/noreg/788-00501.pdf&fromPage=GetDoc.The entire disclosure of this publication is hereby incorporated hereinby reference.

The polymers of the invention may be oil extended with from 5 to about75 percent, preferably from 10 to 60 percent, more preferably from 20 to50 percent, based on total composition weight, of a processing oil.Suitable oils include any oil that is conventionally used inmanufacturing extended EPDM rubber formulations. Examples include bothnaphthenic- and paraffinic-oils.

Rubber formulations of the present invention may be cured usingconventional curing processes include, for example, peroxide curing,sulfur curing, radiation, and combinations thereof. Peroxide curingsystems generally comprise an organic peroxide free radical initiatorand optional coagent. Organic peroxides suitable as free radicalinitiators include, for example, dicumyl peroxide;n-butyl-4,4-di(t-butylperoxy)valerate;1,1-di(t-butylperoxy)3,3,5-trimethylcyclohexane;2,5-dimethyl-2,5-di(t-butylperoxy)hexane; di-t-butyl peroxide; di-t-amylperoxide; t-butyl peroxide; t-butyl cumyl peroxide;2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3;di(2-t-butyl-peroxyisopropyl)benzene; dilauroyl peroxide; dibenzoylperoxide; t-butyl hydroperoxide; and combinations thereof. Suitablecoagents include, for example, metal salts of unsaturated carboxylicacids having from 3 to 8 carbon atoms; unsaturated vinyl compounds andpolyfunctional monomers (e.g., trimethylolpropane trimethacrylate);phenylene bismaleimide; and combinations thereof. Particularly suitablemetal salts include, for example, one or more metal salts of acrylates,diacrylates, methacrylates, and dimethacrylates, wherein the metal isselected from magnesium, calcium, zinc, aluminum, lithium, and nickel.In a particular embodiment, the coagent is selected from zinc salts ofacrylates, diacrylates, methacrylates, and dimethacrylates. In anotherparticular embodiment, the coagent is zinc diacrylate. Sulfur andsulfur-based curing agents with optional accelerators may be used incombination with or in replacement of the peroxide initiators tocrosslink the rubber. Suitable curing agents and accelerators include,for example, sulfur; N-oxydiethylene 2-benzothiazole sulfenamide;N,N-diorthotolylguanidine; bismuth dimethyldithiocarbamate; N-eyclohexyl2-benzothiazole sulfenamide; N,N-diphenylguanidine;4-morpholinyl-2-benzothiazole disulfide; dipentamethylenethiuramhexasulfide; thiuram disulfides; mercaptobenzothiazoles; sulfenamides;dithiocarbamates; thiuram sulfides; guanidines; thioureas; xanthates;dithiophosphates; aldehyde-amines; dibenzothiazyl disulfide;tetraethylthiuram disulfide; tetrabutylthiuram disulfide; andcombinations thereof. High energy radiation sources capable ofgenerating free radicals, such as electron beams, ultra-violetradiation, gamma radiation, X-ray radiation, infrared radiation, heat,and combinations thereof may also be used to crosslink the rubber.

Additional components of the present formulations usefully employedaccording to the present invention include various other ingredients inamounts that do not detract from the properties of the resultantcomposition. These ingredients include, but are not limited to,activators such as calcium or magnesium oxide; fatty acids such asstearic acid and salts thereof; fillers and reinforcers such as calciumor magnesium carbonate, silica, and aluminum silicates; plasticizerssuch as dialkyl esters of dicarboxylic acids; antidegradants; softeners;waxes; and pigments.

Dispersions (both aqueous and non-aqueous) can be formed using thepresent polymers or formulations comprising the same. Frothed foamscomprising the invented polymers can also be formed, as disclosed in PCTPublication No. 2004/027593. The polymers may also be crosslinked by anyknown means, such as the use of peroxide, electron beam, silane, azide,or other cross-linking technique. The polymers can also be chemicallymodified, such as by grafting (for example by the use of maleicanhydride (MAH), silanes, or other grafting agent), halogenation,amination, sulfonation, or other chemical modification.

Additives and adjuvants may be included in any formulation comprisingthe present polymers. Suitable additives include fillers, such asorganic or inorganic particles, including clays, talc, carbon black,titanium dioxide, zeolites, powdered metals, organic or inorganicfibers, including carbon fibers, silicon nitride fibers, steel wire ormesh, and nylon or polyester cording, nano-sized particles, and soforth; tackifiers, oil extenders, including paraffinic or naphthelenicoils; and other natural and synthetic polymers, including other polymersaccording to the invention.

Suitable polymers for blending with the present polymers includethermoplastic and non-thermoplastic polymers including natural andsynthetic polymers. Exemplary polymers for blending includepolypropylene, (both impact modifying polypropylene, isotacticpolypropylene, atactic polypropylene, and random ethylene/propylenecopolymers), conventional poly-4-methyl-1-pentene, various types ofpolyethylene, including high pressure, free-radical LDPE, Ziegler-NattaLLDPE, metallocene PE, such as products disclosed in U.S. Pat. Nos.6,545,088, 6,538,070, 6,566,446, 5,844,045, 5,869,575, and 6,448,341,ethylene-vinyl acetate (EVA), ethylene/vinyl alcohol copolymers,polystyrene, impact modified polystyrene, ABS, styrene/butadiene blockcopolymers and hydrogenated derivatives thereof (SBS and SEBS), andthermoplastic polyurethanes. Homogeneous polymers such as olefinplastomers and elastomers, ethylene and propylene-based copolymers forexample polymers available under the trade designation VERSIFY®commercially available from The Dow Chemical Company and VISTAMAXX®commercially available from ExxonMobil Chemical Company can also beuseful as components in blends comprising the present polymers.

Particularly desirable blends are thermoplastic polyolefin blends (TPO),thermoplastic elastomer blends (TPE), thermoplastic vulcanizates (TPV)and styrenic polymer blends. Polymers of the present invention (bothrigid and flexible) produced via chain-shuttling polymerization can beused to produce TPVs which may have performance and processingcharacteristics comparable or superior to commercially available TPVssuch as Santoprene®, commercially available from Advanced ElastomerSystems, and Sarlink®, commercially available from DSM Elastomers. TPEand TPV blends may be prepared by combining the present multi-blockpolymers, including functionalized or unsaturated derivatives thereofwith an optional rubber, including conventional block copolymers,especially an SBS block copolymer, and optionally a crosslinking orvulcanizing agent. TPO blends are generally prepared by blending thepresent multi-block copolymers with a polyolefin, and optionally acrosslinking or vulcanizing agent.

The foregoing blends may be used in forming a molded object, andoptionally crosslinking the resulting molded article. A similarprocedure using different components has been previously disclosed inU.S. Pat. No. 6,797,779, the entire disclosure of which is herebyincorporated herein by reference.

Suitable conventional block copolymers for this application desirablypossess a Mooney viscosity (ML 1+4 @100° C.) in the range from 10 to135, more preferably from 25 to 100, and most preferably from 30 to 80.Suitable polyolefins especially include linear or low densitypolyethylene, polypropylene (including atactic, isotactic, syndiotacticand impact modified versions thereof) and poly(4-methyl-1-pentene).Suitable styrenic polymers include polystyrene, rubber modifiedpolystyrene (HIPS), styrene/acrylonitrile copolymers (SAN), rubbermodified SAN (ABS or AES) and styrene maleic anhydride copolymers.

In a particularly preferred embodiment, the present invention provides ablend composition comprising a multi-block copolymer and a non-ionomericpolymer. In a particular aspect of this embodiment, the multi-blockcopolymer is selected from ethylene-butene multi-block copolymers andethylene-octene multi-block copolymers. The multi-block copolymer may benon-functionalized or functionalized, for example by maleic, fumaric, oritaconic anhydride grafting or acrylic, methacrylic, or epoxy acrylategrafting. In another particular aspect of this embodiment, thenon-ionomeric polymer is selected from polyamides, polyurethanes,polyureas, polycarbonates, polyesters, polyacrylates, and engineeringthermoplastics. In yet another particular aspect of this embodiment, theblend composition has one or more of the following properties: a Shore Dhardness of from 30 to 80, a flexural modulus of from 10 to 100 kpsi, aneat sphere compression of from 30 to 100, and a coefficient ofrestitution of from 0.650 to 0.850. Particularly suitable blends ofmulti-block copolymers and non-ionomeric polymers are given in Table 2below.

TABLE 2 Example No. 1 2 3 4 5 6 7 8 Rilsan ® AMNO (parts) 50 50 50 50 5050 50 50 ethylene-butene multi-block 10 20 30 0 0 0 0 0 copolymer(parts) ethylene-octene multi-block 0 0 0 30 0 0 0 0 copolymer (parts)0.5% maleic anhydride grafted 0 0 0 0 10 20 30 0 ethylene-butenemulti-block copolymer (parts) 0.5% maleic anhydride grafted 0 0 0 0 0 00 30 ethylene-octene multi-block copolymer (parts) TiO₂ concentrate(phr) 5 5 5 5 5 5 5 5

In another particularly preferred embodiment, multi-block copolymers ofthe present invention are used to produce unique hydrophobic and hybridhydrophilic-hydrophobic block thermoplastic elastomers or thermoplasticvulcanizates with improved elastic recovery and/or higher heatresistance.

In yet another particularly preferred embodiment, the present inventionprovides a blend composition comprising a multi-block copolymer and atleast one ionomeric material, such as acid polymers, partiallyneutralized acid polymers, and highly neutralized acid polymers.Suitable ionomeric materials are further disclosed, for example, in U.S.patent application No. 2005/0049367, the entire disclosure of which ishereby incorporated herein by reference. In a particular aspect of thisembodiment, the multi-block copolymer is selected from ethylene-butenemulti-block copolymers and ethylene-octene multi-block copolymers. Themulti-block copolymer may be non-functionalized or functionalized, forexample by maleic, fumaric, or itaconic anhydride grafting or acrylic,methacrylic, or epoxy acrylate grafting. In another particular aspect ofthis embodiment, the blend composition has one or more of the followingproperties: a Shore D hardness of from 30 to 70, a flexural modulus offrom 10 to 80 kpsi, a neat sphere compression of from 30 to 100, and acoefficient of restitution of from 0.650 to 0.850. Particularly suitableblends of multi-block copolymers and ionomeric polymers are given inTable 3 below.

TABLE 3 Example No. 1 2 3 4 5 6 7 8 Surlyn ® 7940* (parts) 50 50 50 5050 50 50 50 Surly ® 8945** (parts) 40 30 20 20 40 30 20 20ethylene-butene multi-block 10 20 30 0 0 0 0 0 copolymer (parts)ethylene-octene multi-block 0 0 0 30 0 0 0 0 copolymer (parts) 0.5%maleic anhydride grafted 0 0 0 0 10 20 30 0 ethylene-butene multi-blockcopolymer (parts) 0.5% maleic anhydride grafted 0 0 0 0 0 0 0 30ethylene-octene multi-block copolymer (parts) TiO₂ concentrate (phr) 5 55 5 5 5 5 5 *Surlyn ® 7940 is an ethylene/methacrylic acid copolymerpartially neutralized with a lithium-based cation source, and iscommercially available from E. I. du Pont de Nemours and Company.**Surlyn ® 8945 is an acid copolyiner highly neutralized with asodium-based cation source, and is commercially available from E. I. duPont de Nemours and Company.

The blends may be prepared by mixing or kneading the respectivecomponents at a temperature around or above the melt point temperatureof one or both of the components. For most multi-block copolymers, thistemperature may be above 130° C., most generally above 145° C., and mostpreferably above 150° C. Typical polymer mixing or kneading equipmentmay be employed, for example, mills, kneaders, extruders (both singleand twin-screw), Banbury mixers, calenders, and the like. The sequenceof mixing and method may depend on the final composition. A combinationof Banbury batch mixers and continuous mixers may also be employed, suchas a Banbury mixer followed by a mill mixer followed by an extruder.Typically, a TPE or TPV composition will have a higher loading ofcross-linkable polymer (typically the conventional block copolymercontaining unsaturation) compared to TPO compositions. Generally, forTPE and TPV compositions, the weight ratio of block copolymer tomulti-block copolymer may be from about 90:10 to 10:90, more preferablyfrom 80:20 to 20:80, and most preferably from 75:25 to 25:75. For TPOapplications, the weight ratio of multi-block copolymer to polyolefinmay be from about 49:51 to about 5:95, more preferably from 35:65 toabout 10:90. For modified styrenic polymer applications, the weightratio of multi-block copolymer to polymer may also be from about 49:51to about 5:95, more preferably from 35:65 to about 10:90. The ratios maybe changed by changing the viscosity ratios of the various components.There is considerable literature illustrating techniques for changingthe phase continuity by changing the viscosity ratios of theconstituents of a blend.

The blend compositions may contain processing oils, plasticizers, andprocessing aids. Rubber processing oils have a certain ASTM designationsand paraffinic, naphthenic or aromatic process oils are all suitable foruse. Generally from 0 to 150 parts, more preferably 0 to 100 parts, andmost preferably from 0 to 50 parts of oil per 100 parts of total polymerare employed. Higher amounts of oil may tend to improve the processingof the resulting product at the expense of some physical properties.Additional processing aids include conventional waxes, fatty acid salts,such as calcium stearate or zinc stearate, (poly)alcohols includingglycols, (poly)alcohol ethers, including glycol ethers, (poly)esters,including (poly)glycol esters, and metal salt-, especially Group 1 and 2metal or zinc-, salt derivatives thereof.

Compositions, including thermoplastic blends according to the presentinvention may also contain anti-ozonants or anti-oxidants that are knownto those of ordinary skill in the rubber chemistry art. Theanti-ozonants may be physical protectants such as waxy materials thatcome to the surface and protect the part from oxygen or ozone or theymay be chemical protectors that react with oxygen or ozone. Suitablechemical protectors include styrenated phenols, butylated octylatedphenol, butylated di(dimethylbenzyl)phenol, p-phenylenediamines,butylated reaction products of p-cresol and dicyclopentadiene (DCPD),polyphenolic antioxidants, hydroquinone derivatives, quinoline,diphenylene antioxidants, thioester antioxidants, and blends thereof.Some representative trade names of such products are Wingstay® Santioxidant, Polystay® 100 antioxidant, Polystay® 100 AZ antioxidant,Polystay® 200 antioxidant, Wingstay® L antioxidant, Wingstay® LHLSantioxidant, Wingstay® K antioxidant, Wingstay® 29 antioxidant,Wingstay® SN-1 antioxidant, and Irganox antioxidants. In someapplications, the anti-oxidants and anti-ozonants used will preferablybe non-staining and non-migratory.

For providing additional stability against UV radiation, hindered aminelight stabilizers (HALS) and UV absorbers may also be used. Suitableexamples include Tinuvin® 123, Tinuvin® 144, Tinuvin® 622, Tinuvin® 765,Tinuvin® 770, and Tinuvin® 780, commercially available from CibaSpecialty Chemicals, and Chemisorb® T944, available from Cytex Plastics.A Lewis acid may be additionally included with a HALS compound in orderto achieve superior surface quality, as disclosed in U.S. Pat. No.6,051,681.

For some compositions, additional mixing processes may be employed topre-disperse the anti-oxidants, anti-ozonants, UV absorbers, and/orlight stabilizers to form a masterbatch, and subsequently to formpolymer blends therefrom.

Suitable crosslinking agents (also referred to as curing or vulcanizingagents) for use herein include sulfur based, peroxide based, or phenolicbased compounds. Examples of the foregoing materials are found in theart, including in U.S. Pat. Nos. 3,758,643, 3,806,558, 5,051,478,4,104,210, 4,130,535, 4,202,801, 4,271,049, 4,340,684, 4,250,273,4,927,882, 4,311,628 and 5,248,729, the entire disclosures of which arehereby incorporated herein by reference.

When sulfur based curing agents are employed, accelerators and cureactivators may be used as well. Accelerators are used to control thetime and/or temperature required for dynamic vulcanization and toimprove the properties of the resulting cross-linked article. In oneembodiment, a single accelerator or primary accelerator is used. Theprimary accelerator(s) may be used in total amounts ranging from about0.5 to about 4, preferably about 0.8 to about 1.5, phr, based on thetotal composition weight. In another embodiment, combinations of aprimary and a secondary accelerator might be used with the secondaryaccelerator being used in smaller amounts, such as from about 0.05 toabout 3 phr, in order to activate and to improve the properties of thecured article. Combinations of accelerators generally produce articleshaving properties that are somewhat better than those produced by use ofa single accelerator. In addition, delayed action accelerators may beused which are not affected by normal processing temperatures yetproduce a satisfactory cure at ordinary vulcanization temperatures.Vulcanization retarders might also be used. Suitable types ofaccelerators that may be used are amines, disulfides, guanidines,thioureas, thiazoles, thiurams, sulfenamides, dithiocarbamates andxanthates. Preferably, the primary accelerator is a sulfenamide. If asecond accelerator is used, the secondary accelerator is preferably aguanidine, dithiocarbamate or thiuram compound. Certain processing aidsand cure activators such as stearic acid and ZnO may also be used. Whenperoxide based curing agents are used, co-activators or coagents may beused in combination therewith. Suitable coagents includetrimethylolpropane triacrylate (TMPTA), trimethylolpropanetrimethacrylate (TMPTMA), triallyl cyanurate (TAC), triallylisocyanurate (TAIC), among others. Use of peroxide crosslinkers andoptional coagents used for partial or complete dynamic vulcanization areknown in the art and disclosed for example in the publication, “PeroxideVulcanization of Elastomer,” Vol. 74, No. 3, July-August 2001.

When the multi-block copolymer containing composition is at leastpartially crosslinked, the degree of crosslinking may be measured bydissolving the composition in a solvent for specified duration, andcalculating the percent gel or unextractable component. The percent gelnormally increases with increasing crosslinking levels. For curedarticles according to the invention, the percent gel content isdesirably in the range from 5 to 100 percent.

Thermoplastic compositions according to the invention may also containorganic or inorganic fillers or other additives such as starch, talc,calcium carbonate, glass fibers, polymeric fibers (including nylon,rayon, cotton, polyester, and polyaramide), metal fibers, flakes orparticles, expandable layered silicates, phosphates or carbonates, suchas clays, mica, silica, alumina, aluminosilicates or aluminophosphates,carbon whiskers, carbon fibers, nanoparticles including nanotubes,wollastonite, graphite, zeolites, and ceramics, such as silicon carbide,silicon nitride or titanias. Silane based or other coupling agents mayalso be employed for better filler bonding.

The thermoplastic compositions of this invention, including theforegoing blends, may be processed by conventional molding techniquessuch as injection molding, extrusion molding, thermoforming, slushmolding, over molding, insert molding, blow molding, and othertechniques.

Suitable polymer products and methods for their manufacture are furtherdescribed in PCT Publication Nos. WO2005/090425, WO2005/090426, andWO2005/090427, the entire disclosures of which are hereby incorporatedherein by reference.

Golf Ball Applications

Polymer compositions according to the present invention can be used in avariety of applications. For example, the polymer compositions aresuitable for use in golf equipment, including, but not limited to, golfballs, shoes, clubs, and gloves.

In golf balls of the present invention, at least one layer comprises amulti-block copolymer which is prepared in the presence of a chainshuttling agent as described herein. In a particular embodiment, thepolymer is prepared in the presence of a chain shuttling agent asdisclosed in PCT Publication No. WO2005/090425, the entire disclosure ofwhich is hereby incorporated herein by reference. In another particularembodiment, the polymer is prepared in the presence of a chain shuttlingagent as disclosed in PCT Publication No. WO2005/090426, the entiredisclosure of which is hereby incorporated herein by reference. In yetanother particular embodiment, the polymer is prepared in the presenceof a chain shuttling agent as disclosed in PCT Publication No.WO2005/090427, the entire disclosure of which is hereby incorporatedherein by reference.

Compositions of the present invention can be either foamed or filledwith density adjusting materials to provide golf balls having modifiedmoments of inertia.

Golf balls of the present invention can be wound, one-piece, two-piece,or multi-layer balls, so long as at least one layer comprises amulti-block copolymer prepared by a process using a chain shuttlingagent as disclosed herein. In golf balls having two or more layers whichcomprise a multi-block copolymer, the multi-block copolymer of one layermay be the same or a different multi-block copolymer as another layer.The layer(s) comprising the multi-block copolymer can be any one or moreof a core layer, an intermediate layer, or a cover layer.

In a particular embodiment, the invention provides a golf ballcomprising a core having a diameter of from 1.50 inches to 1.62 inchesand a cover having a thickness of from 0.03 inches to 0.19 inches. In aparticular aspect of this embodiment, the core is formed from acomposition comprising a multi-block copolymer produced in the presenceof a chain shuttling agent. In another particular aspect of thisembodiment, the cover is formed from a composition comprising amulti-block copolymer produced in the presence of a chain shuttlingagent.

In another particular embodiment, the invention provides a golf ballcomprising a core having a diameter of from 1.30 inches to 1.62 inches,a cover having a thickness of from 0.02 inches to 0.04 inches, and acasing layer disposed between the core and the cover and having athickness of from 0.03 inches to 0.06 inches. In a particular aspect ofthis embodiment, the core is formed from a composition comprising amulti-block copolymer produced in the presence of a chain shuttlingagent. In another particular aspect of this embodiment, the cover isformed from a composition comprising a multi-block copolymer produced inthe presence of a chain shuttling agent. In yet another particularaspect of this embodiment, the casing layer is formed from a compositioncomprising a multi-block copolymer produced in the presence of a chainshuttling agent.

In another particular embodiment, the invention provides a golf ballcomprising an inner core, an outer core, a cover, and a casing layerdisposed between the outer core and the cover. The inner core preferablyhas a diameter of from 0.50 inches to 1.30 inches. The outer corepreferably has a thickness of from 0.12 inches to 0.55 inches. Thecasing layer preferably has a thickness of from 0.03 inches to 0.06inches. The cover preferably has a thickness of from 0.02 inches to 0.04inches. At least one of the inner core, outer core, cover, and casinglayer is formed from a composition comprising a multi-block copolymerproduced in the presence of a chain shuttling agent.

In yet another particular embodiment, the invention provides amulti-layer ball having a compression molded rubber core, one or moreinjection or compression molded intermediate layer(s), and apolyurethane or polyurea outer cover layer, wherein at least one of theintermediate layer(s) is formed from a composition comprising amulti-block copolymer produced in the presence of a chain shuttlingagent. The polyurethane or polyurea outer cover layer material can bethermoset or thermoplastic. Thermoset materials can be formed into golfball layers by conventional casting or reaction injection moldingtechniques. Thermoplastic materials can be formed into golf ball layersby conventional compression or injection molding techniques. Lightstable polyureas and polyurethanes are preferred for outer cover layermaterials. Preferably, the rubber core composition comprises a baserubber, a crosslinking agent, a filler, a co-crosslinking or initiatoragent, and a cis to trans converting material (e.g., organosulfur andinorganic sulfur compounds). Typical base rubber materials includenatural and synthetic rubbers, including, but not limited to,polybutadiene and styrene-butadiene. The crosslinking agent typicallyincludes a metal salt, such as a zinc salt or magnesium salt, of an acidhaving from 3 to 8 carbon atoms, such as (meth) acrylic acid. Theinitiator agent can be any known polymerization initiator whichdecomposes during the cure cycle, including, but not limited to, dicumylperoxide, 1,1-di-(t-butylperoxy)3,3,5-trimethyl cyclohexane, a-abis-(t-butylperoxy) diisopropylbenzene, 2,5-dimethyl-2,5di-(t-butylperoxy)hexane or di-t-butyl peroxide, and mixtures thereof.Suitable types and amounts of base rubber, crosslinking agent, filler,co-crosslinking agent, and initiator agent are more fully described in,for example, U.S. patent application Publication No. 2003/0144087, theentire disclosure of which is hereby incorporated herein by reference.Reference is also made to U.S. patent application Publication No.2003/0144087 for various ball constructions and materials that can beused in golf ball core, intermediate, and cover layers.

The present invention is not limited by any particular process forforming the golf ball layer(s). It should be understood that thelayer(s) can be formed by any suitable technique, including injectionmolding, compression molding, casting, and reaction injection molding.

Golf balls of the present invention preferably have a coefficient ofrestitution (“COR”) of at least 0.790, more preferably at least 0.800,even more preferably at least 0.805, and most preferably at least 0.810,and a compression of from 75 to 110, preferably from 90 to 100.

For purposes of the present invention, compression is measured accordingto a known procedure, using an Atti compression test device, wherein apiston is used to compress a ball against a spring. The travel of thepiston is fixed and the deflection of the spring is measured. Themeasurement of the deflection of the spring does not begin with itscontact with the ball; rather, there is an offset of approximately thefirst 1.25 mm (0.05 inches) of the spring's deflection. Very lowstiffness cores will not cause the spring to deflect by more than 1.25mm and therefore have a zero compression measurement. The Atticompression tester is designed to measure objects having a diameter of42.7 mm (1.68 inches); thus, smaller objects, such as golf ball cores,must be shimmed to a total height of 42.7 mm to obtain an accuratereading.

For purposes of the present invention, COR is determined according to aknown procedure wherein a golf ball or golf ball subassembly (e.g., agolf ball core) is fired from an air cannon at a given velocity (125ft/s for purposes of the present invention). Ballistic light screens arelocated between the air cannon and the steel plate to measure ballvelocity. As the ball travels toward the steel plate, it activates eachlight screen, and the time at each light screen is measured. Thisprovides an incoming transit time period inversely proportional to theball's incoming velocity. The ball impacts the steel plate and reboundsthough the light screens, which again measure the time period requiredto transit between the light screens. This provides an outgoing transittime period inversely proportional to the ball's outgoing velocity. CORis then calculated as the ratio of the incoming transit time period tothe outgoing transit time period, COR=T_(in)/T_(out).

When numerical lower limits and numerical upper limits are set forthherein, it is contemplated that any combination of these values may beused.

All patents, publications, test procedures, and other references citedherein, including priority documents, are fully incorporated byreference to the extent such disclosure is not inconsistent with thisinvention and for all jurisdictions in which such incorporation ispermitted.

While the illustrative embodiments of the invention have been describedwith particularity, it will be understood that various othermodifications will be apparent to and can be readily made by those ofordinary skill in the art without departing from the spirit and scope ofthe invention. Accordingly, it is not intended that the scope of theclaims appended hereto be limited to the examples and descriptions setforth herein, but rather that the claims be construed as encompassingall of the features of patentable novelty which reside in the presentinvention, including all features which would be treated as equivalentsthereof by those of ordinary skill in the art to which the inventionpertains.

1. A golf ball having at least one layer formed from a compositioncomprising a multi-block copolymer, wherein the multi-block copolymer isproduced by a process comprising: contacting ethylene under additionpolymerization conditions with a catalyst composition, the catalystcomposition comprising the admixture or reaction product resulting fromcombining: (A) a first olefin polymerization catalyst, (B) a secondolefin polymerization catalyst capable of preparing polymers differingin chemical or physical properties from the polymer prepared by thefirst olefin polymerization catalyst under equivalent polymerizationconditions, and (C) a chain shuttling agent, wherein at least one of thefirst olefin polymerization catalyst or the second olefin polymerizationcatalyst is capable of forming a branched polymer by means of chainwalking or reincorporation of in situ formed olefinic polymer chains. 2.The golf ball of claim 1, wherein the composition is a blend comprisingthe multi-block copolymer and a non-ionomeric polymer selected from thegroup consisting of polyamides, polyurethanes, polyureas,polycarbonates, polyesters, polyacrylates, and engineeringthermoplastics.
 3. The golf ball of claim 2, wherein the non-ionomericpolymer is a polyamide.
 4. The golf ball of claim 1, wherein thecomposition is a blend comprising the multi-block copolymer and anadditional polymer selected from acid polymers, partially neutralizedacid polymers, and highly neutralized acid polymers.
 5. The golf ball ofclaim 4, wherein the additional polymer is a partially or highlyneutralized acid polymer and wherein the blend has a Shore D hardness offrom 30 to 80, a flexural modulus of from 10 to 100 kpsi, a neat spherecompression of from 30 to 100, and a coefficient of restitution of from0.650 to 0.850.
 6. The golf ball of claim 1, wherein the golf ball is amulti-layer ball comprising a compression molded rubber core, one ormore injection or compression molded intermediate layer(s), and apolyurethane or polyurea outer cover layer, wherein at least one of theintermediate layer(s) is formed from the composition comprising themulti-block copolymer.
 7. A golf ball having at least one layer formedfrom a composition comprising a multi-block copolymer, wherein themulti-block copolymer is produced by a process comprising: contacting afirst monomer selected from the group consisting of propylene and4-methyl-1-pentene, and one or more addition polymerizable comonomersother than the first monomer, under addition polymerization conditionswith a catalyst composition, the catalyst composition comprising theadmixture or reaction product resulting from combining: (A) a firstolefin polymerization catalyst, (B) a second olefin polymerizationcatalyst capable of preparing polymers differing in chemical or physicalproperties from the polymer prepared by the first olefin polymerizationcatalyst under equivalent polymerization conditions, and (C) a chainshuttling agent.
 8. The golf ball of claim 7, wherein the composition isa blend comprising the multi-block copolymer and a non-ionomeric polymerselected from the group consisting of polyamides, polyurethanes,polyureas, polycarbonates, polyesters, polyacrylates, and engineeringthermoplastics.
 9. The golf ball of claim 8, wherein the non-ionomericpolymer is a polyamide.
 10. The golf ball of claim 7, wherein thecomposition is a blend comprising the multi-block copolymer and anadditional polymer selected from acid polymers, partially neutralizedacid polymers, and highly neutralized acid polymers.
 11. The golf ballof claim 10, wherein the additional polymer is a partially or highlyneutralized acid polymer and wherein the blend has a Shore D hardness offrom 30 to 80, a flexural modulus of from 10 to 100 kpsi, a neat spherecompression of from 30 to 100, and a coefficient of restitution of from0.650 to 0.850.
 12. The golf ball of claim 7, wherein the golf ball is amulti-layer ball comprising a compression molded rubber core, one ormore injection or compression molded intermediate layer(s), and apolyurethane or polyurea outer cover layer, wherein at least one of theintermediate layer(s) is formed from the composition comprising themulti-block copolymer.
 13. A golf ball having at least one layer formedfrom a composition comprising a multi-block copolymer selected from thegroup consisting of maleic anhydride grafted ethylene-butene multi-blockcopolymers and maleic anhydride grafted ethylene-octene multi-blockcopolymers, wherein the multi-block copolymer is produced by a processcomprising: contacting one or more addition polymerizable monomers underaddition polymerization conditions with a catalyst composition, thecatalyst composition comprising the admixture or reaction productresulting from combining: (A) a first olefin polymerization catalyst,(B) a second olefin polymerization catalyst capable of preparingpolymers differing in chemical or physical properties from the polymerprepared by the first olefin polymerization catalyst under equivalentpolymerization conditions, and (C) a chain shuttling agent.
 14. The golfball of claim 13, wherein the composition is a blend comprising themulti-block copolymer and a non-ionomeric polymer selected from thegroup consisting of polyamides, polyurethanes, polyureas,polycarbonates, polyesters, polyacrylates, and engineeringthermoplastics.
 15. The golf ball of claim 14, wherein the non-ionomericpolymer is a polyamide.
 16. The golf ball of claim 13, wherein thecomposition is a blend comprising the multi-block copolymer and anadditional polymer selected from acid polymers, partially neutralizedacid polymers, and highly neutralized polymers.
 17. The golf ball ofclaim 16, wherein the additional polymer is a partially or highlyneutralized acid polymer and wherein the blend has a Shore D hardness offrom 30 to 80, a flexural modulus of from 10 to 100 kpsi, a neat spherecompression of from 30 to 100, and a coefficient of restitution of from0.650 to 0.850.
 18. The golf ball of claim 13, wherein the golf ball isa multi-layer ball comprising a compression molded rubber core, one ormore injection or compression molded intermediate layer(s), and apolyurethane or polyurea outer cover layer, wherein at least one of theintermediate layer(s) is formed from the composition comprising themulti-block copolymer.